WO2015133492A1 - 電池電極用バインダー、およびそれを用いた電極ならびに電池 - Google Patents
電池電極用バインダー、およびそれを用いた電極ならびに電池 Download PDFInfo
- Publication number
- WO2015133492A1 WO2015133492A1 PCT/JP2015/056250 JP2015056250W WO2015133492A1 WO 2015133492 A1 WO2015133492 A1 WO 2015133492A1 JP 2015056250 W JP2015056250 W JP 2015056250W WO 2015133492 A1 WO2015133492 A1 WO 2015133492A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- weight
- battery
- acrylate
- binder
- Prior art date
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 93
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 97
- 239000000178 monomer Substances 0.000 claims abstract description 94
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 239000004094 surface-active agent Substances 0.000 claims abstract description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- -1 alkylene glycol Chemical compound 0.000 claims description 83
- 150000001875 compounds Chemical class 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 24
- 239000011883 electrode binding agent Substances 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 7
- 229920001567 vinyl ester resin Polymers 0.000 claims description 7
- 230000001588 bifunctional effect Effects 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 238000004519 manufacturing process Methods 0.000 description 31
- 238000006116 polymerization reaction Methods 0.000 description 30
- 238000000034 method Methods 0.000 description 26
- 238000011156 evaluation Methods 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000003505 polymerization initiator Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003995 emulsifying agent Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 239000002518 antifoaming agent Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000002482 conductive additive Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- ZUDLIFVTNPYZJH-UHFFFAOYSA-N 1,1,2,2-tetraphenylethylbenzene Chemical compound C1=CC=CC=C1C(C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 ZUDLIFVTNPYZJH-UHFFFAOYSA-N 0.000 description 1
- QIDUHGHFWAMMPV-UHFFFAOYSA-N 1,1-diphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C)C1=CC=CC=C1 QIDUHGHFWAMMPV-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PGRNEGLBSNLPNP-UHFFFAOYSA-N 1,6-dichloro-3-methylhex-1-ene Chemical compound ClC=CC(C)CCCCl PGRNEGLBSNLPNP-UHFFFAOYSA-N 0.000 description 1
- RFQXTZGKFOTWFL-UHFFFAOYSA-N 1-(4-methylphenyl)adamantane Chemical compound C1=CC(C)=CC=C1C1(C2)CC(C3)CC2CC3C1 RFQXTZGKFOTWFL-UHFFFAOYSA-N 0.000 description 1
- BIRJAUKLRAMLEV-UHFFFAOYSA-N 1-phenylethenoxymethylbenzene Chemical compound C=1C=CC=CC=1C(=C)OCC1=CC=CC=C1 BIRJAUKLRAMLEV-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-O 2,3-dimethylimidazolium ion Chemical compound CC1=[NH+]C=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-O 0.000 description 1
- QZLAEIZEPJAELS-UHFFFAOYSA-N 2,4,4-trimethylpentane-2-thiol Chemical compound CC(C)(C)CC(C)(C)S QZLAEIZEPJAELS-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- NDQHSZGNIRQZEK-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoyloxymethyl)butanedioic acid Chemical compound C(C=C)(=O)OCC(C(=O)O)(CC(=O)O)CC NDQHSZGNIRQZEK-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BHYVPLASKPLRRX-UHFFFAOYSA-N 2-methyl-1-pyrrolidin-1-ylpropan-1-imine Chemical compound CC(C)C(=N)N1CCCC1 BHYVPLASKPLRRX-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- NDAJNMAAXXIADY-UHFFFAOYSA-N 2-methylpropanimidamide Chemical compound CC(C)C(N)=N NDAJNMAAXXIADY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- PMZVSHSZVKFXMZ-UHFFFAOYSA-N 2-phenylmethoxyprop-2-enamide Chemical compound NC(=O)C(=C)OCC1=CC=CC=C1 PMZVSHSZVKFXMZ-UHFFFAOYSA-N 0.000 description 1
- NYVPRWODADOGAO-UHFFFAOYSA-N 2-phenylmethoxyprop-2-enenitrile Chemical compound N#CC(=C)OCC1=CC=CC=C1 NYVPRWODADOGAO-UHFFFAOYSA-N 0.000 description 1
- BTYIFQSAIPDZQW-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole Chemical compound CC(C)C1=NCCN1 BTYIFQSAIPDZQW-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- FVCPXLWAKNJIKK-UHFFFAOYSA-N Dimexano Chemical compound COC(=S)SSC(=S)OC FVCPXLWAKNJIKK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- VOOVDZMAQQVAEW-PFONDFGASA-N [(z)-2-methyl-4-phenylpent-3-en-2-yl]benzene Chemical compound C=1C=CC=CC=1C(/C)=C\C(C)(C)C1=CC=CC=C1 VOOVDZMAQQVAEW-PFONDFGASA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- NKKMVIVFRUYPLQ-NSCUHMNNSA-N crotononitrile Chemical compound C\C=C\C#N NKKMVIVFRUYPLQ-NSCUHMNNSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 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
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 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
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003151 propanoic acid esters Chemical class 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate 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
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/287—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polypropylene oxide in the alcohol moiety
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a binder used for an electrode of a battery, an electrode manufactured using the binder, and a battery manufactured using the electrode.
- the battery includes an electrochemical capacitor and is a primary battery or a secondary battery.
- Specific examples of the battery are a lithium ion secondary battery and a nickel metal hydride secondary battery.
- Lithium ion secondary batteries have high energy density and high voltage, and are therefore used in electronic devices such as mobile phones, notebook computers, and camcorders. Recently, due to heightened awareness of environmental protection and the development of related laws, applications as in-vehicle applications such as electric vehicles and hybrid electric vehicles and storage batteries for household power storage are also progressing.
- a lithium ion secondary battery is generally composed of a negative electrode, a positive electrode, a separator, an electrolytic solution, and a current collector.
- the negative electrode is coated on a current collector typified by copper foil with a negative electrode active material such as graphite or hard carbon capable of inserting and removing lithium ions, a conductive additive, a binder, and a solvent. Obtained by drying.
- a negative electrode active material such as graphite or hard carbon capable of inserting and removing lithium ions
- a conductive additive such as graphite or hard carbon capable of inserting and removing lithium ions
- a conductive additive such as graphite or hard carbon
- a binder styrene-butadiene rubber
- the positive electrode is made by mixing a layered positive electrode active material such as lithium cobaltate or spinel type lithium manganate with a conductive auxiliary such as carbon black, a binder such as polyvinylidene fluoride or polytetrafluoroethylene, and the like.
- the coating liquid dispersed in such a polar solvent is manufactured by applying and drying on a current collector foil represented by an aluminum foil in the same manner as the negative electrode.
- binders of lithium ion batteries need to increase the amount of the binder added in order to secure the binding force, and a decrease in performance due to this is a problem.
- N-methylpyrrolidone is used as a slurry solvent, and an aqueous binder is desired from the viewpoint of recovery, cost, toxicity and environmental load.
- the binder of the positive electrode still uses polyvinylidene fluoride or polytetrafluoroethylene using N-methylpyrrolidone as a dispersion solvent as a binder, and binds the current collector to the active material or between the active materials.
- Patent Documents 1 and 2 disclose a binder containing a copolymer composed of aromatic vinyl, conjugated diene, ethylenically unsaturated carboxylic acid ester and unsaturated carboxylic acid (Patent Document 1), and A binder comprising a polymer aqueous dispersion selected from styrene-butadiene polymer latex and acrylic emulsion is proposed (Patent Document 2).
- Patent Documents 3 and 4 a binder containing a copolymer composed of aromatic vinyl, conjugated diene, (meth) acrylic acid ester and ethylenically unsaturated carboxylic acid (Patent Document 3), and bifunctional (meth)
- the binder (patent document 4) containing the polymer containing an acrylate is proposed.
- these binders are used for electrodes (positive electrode and / or negative electrode)
- the capacity of the charge / discharge cycle decreases under high temperature conditions.
- the present invention has been made in view of the above circumstances, and has a water-based binder with a low environmental load, which has excellent electrode slurry coating properties, high binding properties, and does not cause oxidative degradation in an electrode environment (especially in a positive electrode environment).
- An object is to provide an electrode and a battery using the same.
- the present inventors As a result of repeated studies to achieve the above object, the present inventors, as a result, a structural unit derived from a (meth) acrylate monomer having a hydroxyl group, a structural unit derived from a polyfunctional (meth) acrylate monomer, By using a binder containing a polymer containing a reactive surfactant, the present inventors have found that the above problems can be solved, and have made the present invention. That is, the present invention relates to the following.
- the (meth) acrylate monomer (A) having a hydroxyl group has the general formula: (Wherein R 1 is hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, R 2 and R 3 are each hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, and n is (It is an integer from 1 to 30.)
- the polyfunctional (meth) acrylate monomer (B) has the formula: (Wherein R 11 s are the same or different and each represents hydrogen or a methyl group; R 12 is a pentavalent or lower organic group having 2 to 100 carbon atoms, m is an integer of 5 or less. )
- the polymer is (IV) a structural unit derived from a (meth) acrylic acid ester monomer and / or an organic acid vinyl ester monomer (D);
- the (meth) acrylic acid ester monomer (D) has the formula: Wherein R 21 is hydrogen or a methyl group, R 22 is a hydrocarbon group having 1 to 50 carbon atoms.
- a compound represented by The (meth) acrylic acid monomer (E) has the formula: (In the formula, R 31 is hydrogen or a methyl group.)
- the amount of structural units derived from the monomers (A) to (E) is (A) 10-90 wt%, (B) 1-70 wt%, (C) 0.01-25 wt%, (D) 0-70 wt% and (E) 0-70 wt% [1 ]
- the binder for battery electrodes according to any one of [9] to [9].
- a battery electrode comprising the binder according to any one of [1] to [11] and an active material.
- [13] [12] A battery comprising the electrode according to [12].
- the binder of this invention is excellent in binding property with an active material, a conductive support agent, and a current collector. Excellent binding properties (strong binding properties) are due to the large surface area of the polymer fine particles dispersed in water and the use of structural units derived from (meth) acrylate monomers having hydroxyl groups. It is thought that.
- the binder of the present invention provides an electrode having excellent flexibility.
- the binder of the present invention is suppressed from being dissolved in the electrolytic solution and is not substantially dissolved in the electrolytic solution. This insolubility is considered to be due to a highly crosslinked structure by using a structural unit derived from a polyfunctional (meth) acrylate monomer as a crosslinking agent component.
- the binder of the present invention uses a reactive surfactant for emulsification, and since the surfactant becomes a part of the polymer, foaming of the dispersion solvent is reduced, and the defoaming operation at the time of slurry preparation is simplified. It can be performed.
- the binder of the present invention is excellent in dispersibility.
- the present invention can provide a battery having a high capacity and a long battery life, particularly a secondary battery.
- the secondary battery is excellent in charge / discharge cycle characteristics.
- the secondary battery is excellent in long-term cycle life and cycle charge / discharge characteristics at a high temperature (for example, 60 ° C.).
- the secondary battery of the present invention can be used at a high voltage and has excellent heat resistance. Since the binder is water-based (the medium is water), the burden on the environment is small and no organic solvent recovery device is required.
- the binder of the present invention comprises (I) a structural unit derived from a (meth) acrylate monomer (A) having a hydroxyl group, (II) a structural unit derived from a polyfunctional (meth) acrylate monomer (B); (III) A battery electrode binder comprising a polymer containing a structural unit derived from a reactive surfactant (C).
- the (meth) acrylate monomer (A) having a hydroxyl group is preferably an alkylene glycol mono (meth) acrylate having a molecular weight (number average molecular weight) of 100 to 1000 (for example, 150 to 1000).
- the (meth) acrylate monomer (A) having a hydroxyl group has a general formula: (Wherein R 1 is hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, R 2 and R 3 are each hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, and n is (It is an integer from 1 to 30.) It is preferable that it is a compound shown by these. n is an integer of 1 to 30. Preferably n is an integer of 2 to 25, more preferably 4 to 20.
- the (meth) acrylate monomer (A) having a hydroxyl group include hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and Examples include polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. These can be used alone or in combination of two or more.
- tetraethylene glycol mono (meth) acrylate tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate are preferable.
- the polyfunctional (meth) acrylate monomer (B) works as a crosslinking agent.
- examples of the polyfunctional (meth) acrylate monomer include bifunctional to pentafunctional (meth) acrylate.
- a bifunctional to pentafunctional cross-linking agent is excellent in dispersion by emulsion polymerization, and has excellent physical properties (flexibility and binding properties) as a binder.
- the polyfunctional (meth) acrylate monomer is preferably a trifunctional or tetrafunctional (meth) acrylate.
- the polyfunctional (meth) acrylate monomer (B) has the formula: (Wherein R 11 s are the same or different and each represents hydrogen or a methyl group; R 12 is a pentavalent or lower organic group having 2 to 100 carbon atoms, m is an integer of 5 or less. ) It is preferable that it is a compound shown by these.
- R 12 is a divalent to pentavalent organic group, and m is an integer of 2 to 5. More preferably, R 12 is 3-5 valence, in particular 3-4 divalent organic group, m is 3-5 integer, in particular 3-4 integer.
- R 12 is a hydrocarbon group, an oxyalkylene group (— (OA 1 ) —, A 1 is an alkylene group having 2 to 4 carbon atoms), a polyoxyalkylene group (— (OA 2 ) p —, and A 2 is a carbon number 2 to 4 alkylene groups, p is 2 to 30), or two or more of these may be included simultaneously.
- R 12 may contain a substituent.
- substituents include a hydroxyl group, a carboxylic acid group, a nitrile group, a fluorine atom, an amino group, a sulfonic acid group, a phosphoric acid group, an amide group, an isocyanuric acid group, an oxyalkylene group (-(OA 3 ) -H, A 3 is an alkylene group having 2 to 4 carbon atoms), a polyoxyalkylene group (— (OA 4 ) q —H, A 4 is an alkylene group having 2 to 4 carbon atoms, and q is 2 to 30), alkoxy An oxyalkylene group (-(A 5 -O) -B 1 , A 5 is an alkylene group having 2 to 4 carbon atoms, B 1 is an alkyl group having 1 to 4 carbon atoms), an alkoxy polyoxyalkylene group (-(A 6 -O) r -B 2 and A 6 are alkylene groups having 2 to 4 carbon atoms
- bifunctional (meth) acrylate monomer examples include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol Examples include di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, dioxane glycol di (meth) acrylate, and bis (meth) acryloyloxyethyl phosphate.
- trifunctional (meth) acrylate monomer examples include trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-added tri (meth) acrylate, trimethylolpropane PO-added tri (meth) acrylate, and pentaerythritol tri (meth).
- tetrafunctional (meth) acrylate monomer examples include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol EO-added tetra (meth) acrylate.
- pentafunctional (meth) acrylate monomers include dipentaerythritol penta (meth) acrylate.
- the polyfunctional (meth) acrylate monomer may be one type, or two or more types may be used in combination.
- the amount of the structural unit of the polyfunctional (meth) acrylate monomer (B) is 0.5 to 100 parts by weight, for example, 1 to 95, relative to 100 parts by weight of the structural unit of the (meth) acrylate monomer (A) having a hydroxyl group. It may be by weight, in particular 2 to 90 parts by weight, in particular 3 to 70 parts by weight.
- the reactivity of the reactive surfactant (C) means that it contains a reactive double bond and undergoes a polymerization reaction with the monomer and the reactive surfactant. That is, the reactive surfactant (C) acts as an emulsifier for the monomer in the polymerization for producing the polymer, and is covalently incorporated into a part of the polymer after the polymerization. Therefore, the emulsion polymerization and the dispersion of the produced polymer are good, and the physical properties (flexibility, binding property) as a binder are excellent. Further, since the reactive surfactant becomes a part of the polymer, the reactive surfactant is not liberated, so that the dissolution of the surfactant in the electrolytic solution is suppressed, and the battery performance is improved.
- the reactive surfactant (C) generally has a compound having a (polymerizable) ethylenically unsaturated double bond and a group exhibiting surface activity, in particular, an ethylenically unsaturated double bond and a surface active property.
- a compound in which groups are directly bonded In the reactive surfactant (C), a displaceable group or atom (for example, a hydrogen atom) in the surfactant is replaced with a group having an ethylenically unsaturated double bond (for example, a vinyl group or an allyl group).
- a compound is preferred.
- Surfactant means a compound (preferably a normal surfactant) that exhibits surfactant properties, such as an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
- the molecular weight (number average molecular weight) of the reactive surfactant (C) may be 100 to 15,000, preferably 150 to 5,000.
- the reactive surfactant examples include a reactive anionic surfactant, a reactive nonionic surfactant, a reactive cationic surfactant, and a reactive amphoteric surfactant.
- a reactive anionic surfactant and a reactive nonionic surfactant are preferred, and a reactive anionic surfactant is particularly preferred.
- the reactive anionic surfactant include sulfate ester type, sulfonic acid type, carboxylic acid type, and phosphate ester type alkali metal salts, alkaline earth metal salts, alkanolamine salts, ammonium salts, and the like.
- Sulfuric acid ester type, phosphoric acid ester type, and carboxylic acid type are preferable, and sulfuric acid ester type is particularly preferable.
- Specific examples of the sulfate ester type include Latemul PD-104, 105 (manufactured by Kao Corporation), Adekari Soap SR (manufactured by Adeka Company), Aqualon HS (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Aqualon KH (Daiichi Kogyo Pharmaceutical Co., Ltd.) Manufactured), Eleminol RS (manufactured by Sanyo Chemical Co., Ltd.), Antox EMH, and the like.
- Reactive nonionic surfactants include polyoxyalkylene alkenyl ether, polyoxyethylene alkylpropenyl phenyl ether, ⁇ -hydro- ⁇ - (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy- 1,2-ethanediyl) and the like.
- Specific examples include Latemul PD-420, 430, 450 (manufactured by Kao), Adekaria soap ER (manufactured by Adeka), Aqualon RN (manufactured by Daiichi Kogyo Seiyaku), and the like.
- the reactive surfactant may be one type or two or more types can be used in combination.
- the amount of the structural unit of the reactive surfactant (C) may be an amount generally used in the emulsion polymerization method. Specifically, it is in the range of 0.01 to 25% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 2015% by weight, based on the total amount of monomers charged.
- the polymer of the present invention is: (I) a structural unit derived from a (meth) acrylate monomer having a hydroxyl group (A), (II) a structural unit derived from a polyfunctional (meth) acrylate monomer (B), and (III) a reactive surfactant ( In addition to the structural units derived from C) (IV) a structural unit derived from a (meth) acrylic acid ester monomer and / or an organic acid vinyl ester monomer (D); (V) One or both of structural units derived from the (meth) acrylic acid monomer (E) may be included.
- the polymer of the present invention may have the following structural units.
- each of the monomers (A) to (E) may be one kind or a combination of two or more kinds. It is possible to use other monomers other than the monomers (A) to (E).
- the (meth) acrylic acid ester monomer (D) has the formula: Wherein R 21 is hydrogen or a methyl group, R 22 is a hydrocarbon group having 1 to 50 carbon atoms. ) It is preferable that it is a compound shown by these.
- R 22 is a monovalent organic group, and may be a saturated or unsaturated aliphatic group (for example, a chain aliphatic group or a cyclic aliphatic group), an aromatic group, or an araliphatic group.
- R 22 is preferably a saturated hydrocarbon group, particularly a saturated aliphatic group.
- the R 22 group is particularly preferably a branched or straight chain alkyl group.
- R 22 has from 1 to 50 carbon atoms, for example from 1 to 30, in particular from 1 to 20, in particular from 1 to 10.
- (meth) acrylic acid ester monomer (D) examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n.
- methyl (meth) acrylate Preferred are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. .
- These (meth) acrylic acid ester monomers can be used alone or in combination of two or more.
- R 23 is a monovalent organic group, and may be a saturated or unsaturated aliphatic group (for example, a chain aliphatic group or a cyclic aliphatic group), an aromatic group, or an araliphatic group.
- R 23 is preferably a saturated hydrocarbon group, particularly a saturated aliphatic group.
- the R 23 group is particularly preferably a branched or straight chain alkyl group.
- R 23 has 1 to 50 carbon atoms, for example 1 to 30, in particular 1 to 20.
- organic acid vinyl ester monomer (D) examples include vinyl acetate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate. It is done. Of these, vinyl acetate and vinyl propionate are preferable. These can be used alone or in combination of two or more.
- the (meth) acrylic acid monomer (E) has the formula: (In the formula, R 31 is hydrogen or a methyl group.) It is preferable that it is a compound shown by these.
- (meth) acrylic acid monomer (E) examples include methacrylic acid and acrylic acid, which can be used alone or in combination of two or more. Two combinations of methacrylic acid and acrylic acid may be used in a weight ratio of 1:99 to 99: 1, for example 5:95 to 95: 5, in particular 20:80 to 80:20.
- vinyl monomers include monomers that are gaseous at standard conditions, specifically ethylene, propylene, vinyl chloride, and monomers that are liquid or solid at standard conditions, particularly monomers (A), (B), ( (Meth) acrylic monomers other than C), (D) and (E), for example, (meth) acrylic monomers having a hydroxyl group, an amide group, a fluorine atom, a sulfonic acid group, a phosphoric acid group or the like as a substituent. It is done.
- the monomers used are ethylenically unsaturated double groups contained in the (meth) acrylic group.
- the amount of structural units derived from the monomers (A) to (E) is: With respect to 100 parts by weight of the constituent unit of the (meth) acrylate monomer (A) having a hydroxyl group, (B) 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 2 to 70 parts by weight, (C) 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 2 to 70 parts by weight, (D) 0 to 500 parts by weight, preferably 1 to 400 parts by weight, more preferably 2 to 300 parts by weight, and (E) 0 to 100 parts by weight, preferably 0.5 to 80 parts by weight, more preferably 1 It may be up to 50 parts by weight.
- the amount of structural units derived from monomers (A) to (E) is (A) 10-90 wt%, (B) 1-70 wt%, (C) 0.01-25 wt%, (D) 0-70 wt%, and (E) 0-70 wt%, Preferably (A) 20 to 80% by weight, (B) 2 to 50% by weight, (C) 0.05 to 20% by weight, (D) 0 to 60% by weight and (E) 0 to 60% by weight.
- the upper limit of the total amount of structural units derived from monomer (D) and monomer (E) may be 70% by weight, for example 60% by weight, in particular 50% by weight, and the lower limit is 0% by weight, for example 0.00%. It may be 1% by weight.
- the amount of other monomers may be up to 40% by weight, for example 0-20% by weight, in particular 0.1-15% by weight, based on the polymer.
- a general emulsion polymerization method As a method for obtaining the polymer of the present invention, a general emulsion polymerization method, a seed polymerization method, a method in which a monomer or the like is swollen in seed particles, and a polymerization method can be used.
- a composition containing a monomer, a reactive surfactant, a polymerization initiator, water, and optionally a dispersant, a chain transfer agent, a pH adjuster, etc. at room temperature in a closed container equipped with a stirrer and a heating device. Is stirred in an inert gas atmosphere to emulsify monomers and the like in water.
- a method using stirring, shearing, ultrasonic waves, or the like can be applied, and a stirring blade, a homogenizer, or the like can be used. Subsequently, the temperature is raised while stirring to initiate polymerization, whereby a spherical polymer emulsion (aqueous dispersion) in which the polymer is dispersed in water can be obtained.
- a spherical polymer emulsion aqueous dispersion
- the produced spherical polymer may be separately isolated and then dispersed in an organic solvent such as N-methylpyrrolidone using a dispersant or the like.
- a method of obtaining a polymer emulsion by again dispersing in water using a monomer, an emulsifier, a dispersant and the like.
- the monomer addition method at the time of polymerization may be monomer dropping, pre-emulsion dropping, or the like in addition to batch preparation, and two or more of these methods may be used in combination.
- the particle structure of the polymer in the binder of the present invention is not particularly limited.
- a polymer emulsion containing core-shell composite polymer particles produced by seed polymerization can be used.
- the seed polymerization method for example, a method described in “Dispersion / Emulsification System Chemistry” (Publisher: Engineering Books Co., Ltd.) can be used. Specifically, it is a method of growing a core particle by adding a monomer, a polymerization initiator, and a reactive surfactant to a system in which seed particles produced by the above method are dispersed. The above method is repeated once or more. Also good.
- particles using the polymer of the present invention or a known polymer may be employed.
- the known polymer include polyethylene, polypropylene, polyvinyl alcohol, polystyrene, poly (meth) acrylate, and polyether, but are not limited, and other known polymers can be used. Further, one kind of homopolymer or two or more kinds of copolymers or blends may be used.
- the particle shape of the polymer in the binder of the present invention includes a plate shape, a hollow structure, a composite structure, a localized structure, a daruma-shaped structure, an octopus-like structure, a raspberry-like structure, and the like. Particles having two or more types of structures and compositions can be used without departing from the scope.
- the reactive surfactant functions as an emulsifier.
- an emulsifier that does not have a reactive group (particularly an ethylenically unsaturated double bond) may be used in addition to a reactive surfactant. It is preferable not to use it.
- the polymerization initiator used in the present invention is not particularly limited, and a polymerization initiator generally used in an emulsion polymerization method can be used. Specific examples thereof include water-soluble polymerization initiators represented by persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, and oil-soluble polymerization represented by cumene hydroperoxide and diisopropylbenzene hydroperoxide.
- persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate
- oil-soluble polymerization represented by cumene hydroperoxide and diisopropylbenzene hydroperoxide.
- Initiator hydroperoxide, 4-4′-azobis (4-cyanovaleric acid), 2-2′-azobis [2- (2-imidazolin-2-yl) propane, 2-2′-azobis (propane- 2-Carboamidine) 2-2'-azobis [N- (2-carboxyethyl) -2-methylpropanamide, 2-2'-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazoline- 2-yl] propane ⁇ , 2-2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) and 2-2′-azobis ⁇ 2- And azo initiators such as methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propanamide ⁇ , redox initiators, and the like. These polymerization initiators may be used alone or in combination of two or more.
- the amount of the polymerization initiator used in the present invention may be an amount generally used in the emulsion polymerization method. Specifically, it is in the range of 0.01 to 5% by weight, preferably 0.05 to 3% by weight, more preferably 0.1 to 1% by weight, based on the amount of monomer charged.
- the water used for producing the binder of the present invention is not particularly limited, and generally used water can be used. Specific examples thereof include tap water, distilled water, ion exchange water, and ultrapure water. Among these, distilled water, ion exchange water, and ultrapure water are preferable.
- a dispersant can be used as necessary, and the kind and amount of use are not particularly limited, and a commonly used dispersant can be freely used in an arbitrary amount.
- Specific examples include sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, polyacrylic acid or its sodium salt, polyethyleneimine, acrylic acid / maleic acid copolymer or its sodium salt, and the like. These dispersants can be used alone or in admixture of two or more.
- a chain transfer agent can be used as necessary.
- the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, 2,4-diphenyl-4 -Xanthogen compounds such as methyl-1-pentene, 2,4-diphenyl-4-methyl-2-pentene, dimethylxanthogen disulfide, diisopropylxanthogen disulfide, terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram Thiuram compounds such as monosulfide, phenol compounds such as 2,6-di-t-butyl
- the polymerization time and polymerization temperature are not particularly limited. Although it can be appropriately selected depending on the type of polymerization initiator used, etc., the polymerization temperature is generally 20 to 100 ° C., and the polymerization time is 0.5 to 100 hours.
- the polymer obtained by the above method can be adjusted in pH by using a base as a pH adjuster as necessary.
- a base include alkali metal (Li, Na, K, Rb, Cs) hydroxide, ammonia, an inorganic ammonium compound, an organic amine compound, and the like.
- the pH range is pH 1 to 11, preferably pH 2 to 11, more preferably pH 2 to 10, such as pH 3 to 10, especially pH 4 to 9.
- the binder of the present invention may generally be a binder composition containing a polymer and water, particularly a binder composition in which the polymer is dispersed in water.
- the content (solid content concentration) of the polymer in the binder of the present invention is 1 to 80% by weight, preferably 5 to 70% by weight, more preferably 10 to 60% by weight.
- the particle diameter of the polymer in the binder of the present invention can be measured by a dynamic light scattering method, a transmission electron microscope method, an optical microscope method, or the like.
- the average particle size calculated from the scattering intensity obtained using the dynamic light scattering method is 0.001 ⁇ m to 1 ⁇ m, preferably 0.001 ⁇ m to 0.500 ⁇ m.
- Specific examples of the measuring device include Spectris Zetasizer Nano.
- the method for preparing slurry for battery electrode using the binder of the present invention is not particularly limited, and the binder, active material, conductive additive, water, thickener as necessary, etc. of the present invention May be dispersed using an ordinary stirrer, disperser, kneader, planetary ball mill, homogenizer, or the like. In order to increase the efficiency of dispersion, heating may be performed within a range that does not affect the material.
- an antifoaming agent may be added to the binder composition in advance or may be added to the battery electrode slurry liquid.
- an antifoaming agent When an antifoaming agent is added, the dispersibility of each component is improved when the slurry for battery electrodes is prepared, and the coating property of the slurry is improved (where the bubbles remain in the coating), and bubbles remain on the electrode. Can be suppressed.
- antifoaming agents include silicone-based antifoaming agents, mineral oil-based antifoaming agents, and polyether-based antifoaming agents. Silicone and mineral oil defoamers are preferred.
- silicone-based antifoaming agent examples include dimethylsilicone-based, methylphenylsilicone-based, and methylvinylsilicone-based antifoaming agents, preferably dimethylsilicone-based. These antifoaming agents can be used alone or in admixture of two or more.
- the production method of the battery electrode is not particularly limited, and a general method is used.
- a preparation solution (coating solution) for a battery electrode slurry composed of a positive electrode active material or a negative electrode active material, a conductive additive, a binder, water, and a thickener as necessary may be a doctor blade method, applicator method, silk It is carried out by uniformly applying an appropriate thickness on the current collector surface by a screen method or the like.
- a negative electrode active material powder, a positive electrode active material powder, a conductive additive, a binder, etc. are dispersed in water to form a slurry, which is applied to a metal electrode substrate (that is, a current collector) and then a predetermined slit. Uniform to an appropriate thickness with a blade having a width.
- the electrode is dried in, for example, hot air at 100 ° C. or vacuum at 80 ° C. in order to remove excess water and organic solvent.
- An electrode material is manufactured by press-molding the dried electrode with a pressing device. You may heat-process again after pressing, and may remove water, a solvent, an emulsifier, etc.
- the positive electrode material is, for example, a metal electrode substrate as an electrode material substrate, a positive electrode active material on the metal electrode substrate, and an exchange of good ions with the electrolyte layer, and a conductive auxiliary agent and a positive electrode active material on the metal substrate. It consists of a binder for fixing.
- aluminum is used for the metal electrode substrate of the positive electrode material, but is not limited thereto, and may be nickel, stainless steel, gold, platinum, titanium, or the like.
- the positive electrode active material used in the present invention is a lithium metal-containing composite oxide powder having any composition of LiMO 2 , LiM 2 O 4 , Li 2 MO 3 , and LiMEO 4 .
- M in the formula is mainly composed of a transition metal and includes at least one of Co, Mn, Ni, Cr, Fe, and Ti.
- M is made of a transition metal, but Al, Ga, Ge, Sn, Pb, Sb, Bi, Si, P, B, etc. may be added in addition to the transition metal.
- E contains at least one of P and Si.
- the particle diameter of the positive electrode active material is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less. These active materials have an electromotive force of 3 V (vs. Li / Li +) or more.
- positive electrode active material examples include lithium cobaltate, lithium nickelate, nickel / manganese / lithium cobaltate (ternary system), spinel type lithium manganate, and lithium iron phosphate.
- the negative electrode material is, for example, a metal electrode substrate as an electrode material substrate, a negative electrode active material on the metal electrode substrate, and exchange of good ions with the electrolyte layer, and the conductive auxiliary agent and the negative electrode active material are fixed to the metal substrate It is made up of a binder.
- copper is used for the metal electrode substrate, but is not limited thereto, and may be nickel, stainless steel, gold, platinum, titanium, or the like.
- the negative electrode active material used in the present invention is a carbon material (natural graphite, artificial graphite, amorphous carbon, etc.) having a structure (porous structure) capable of occluding and releasing lithium ions, or occluding and releasing lithium ions. It is a powder made of a metal such as lithium, aluminum-based compound, tin-based compound, silicon-based compound, and titanium-based compound. The particle diameter is preferably from 10 nm to 100 ⁇ m, more preferably from 20 nm to 20 ⁇ m. Moreover, you may use as a mixed active material of a metal and a carbon material. It is preferable to use a negative electrode active material having a porosity of about 70%.
- the conductive aid include conductive carbon black such as graphite, furnace black, acetylene black, and ketjen black, or metal powder. These conductive aids may be used alone or in combination of two or more.
- the thickener examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, and sodium salts, ammonium salts, polyvinyl alcohol, and polyacrylates thereof. These thickeners may be used alone or in combination of two or more.
- the following battery manufacturing method is mainly a lithium ion secondary battery manufacturing method.
- the manufacturing method of the battery in particular, the secondary battery is not particularly limited, and includes a positive electrode, a negative electrode, a separator, an electrolytic solution, and a current collector, and is manufactured by a known method.
- a positive electrode, a separator, and a negative electrode are inserted into an outer can. This is impregnated with an electrolytic solution. Then, it joins with a sealing body by tab welding etc., a sealing body is enclosed, and a storage battery is obtained by crimping.
- the shape of the battery is not limited, but examples include a coin type, a cylindrical type, and a sheet type, and a structure in which two or more batteries are stacked may be used.
- a positive electrode and a negative electrode are directly contacted to prevent short circuit in the battery, and a known material can be used. Specifically, it is made of a porous polymer film such as polyolefin or paper.
- a porous polymer film such as polyolefin or paper.
- a film such as polyethylene or polypropylene is preferable because it is not affected by the electrolytic solution.
- the electrolytic solution is a solution comprising an electrolyte lithium salt compound and an aprotic organic solvent as a solvent.
- the electrolyte lithium salt compound a lithium salt compound having a wide potential window, which is generally used in lithium ion batteries, is used.
- aprotic organic solvents examples include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, ⁇ -butyrolactone, tetrahydrofuran, 1,3-dioxolane, Linear ethers such as dipropyl carbonate, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, propyl nitrile, anisole, acetic acid ester, propionic acid ester, diethyl ether can be used. Good.
- a room temperature molten salt can be used as the solvent.
- the room temperature molten salt refers to a salt that is at least partially in a liquid state at room temperature, and the room temperature refers to a temperature range in which a power supply is assumed to normally operate.
- the temperature range in which the power supply is assumed to operate normally has an upper limit of about 120 ° C., in some cases about 60 ° C., and a lower limit of about ⁇ 40 ° C., in some cases about ⁇ 20 ° C.
- the room temperature molten salt is also called an ionic liquid and is a “salt” composed of only ions (anions and cations), and in particular, a liquid compound is called an ionic liquid.
- quaternary ammonium organic cation examples include imidazolium ions such as dialkylimidazolium and trialkylimidazolium, tetraalkylammonium ions, alkylpyridinium ions, pyrazolium ions, pyrrolidinium ions, and piperidinium ions.
- imidazolium ions such as dialkylimidazolium and trialkylimidazolium, tetraalkylammonium ions, alkylpyridinium ions, pyrazolium ions, pyrrolidinium ions, and piperidinium ions.
- an imidazolium cation is preferable.
- tetraalkylammonium ions include, but are not limited to, trimethylethylammonium ion, trimethylethylammonium ion, trimethylpropylammonium ion, trimethylhexylammonium ion, tetrapentylammonium ion, and triethylmethylammonium ion. is not.
- the alkylpyridinium ions include N-methylpyridinium ion, N-ethylpyridinium ion, N-propylpyridinium ion, N-butylpyridinium ion, 1-ethyl-2methylpyridinium ion, 1-butyl-4-methyl Examples thereof include, but are not limited to, pyridinium ions and 1-butyl-2,4 dimethylpyridinium ions.
- Examples of the imidazolium cation include 1,3-dimethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-methyl-3-ethylimidazolium ion, 1-methyl-3-butylimidazolium ion, 1- Butyl-3-methylimidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2-dimethyl-3-ethylimidazolium ion, 1,2-dimethyl-3-propylimidazolium ion, 1-butyl- Examples include 2,3-dimethylimidazolium ion, but are not limited thereto.
- anionic species include halide ions such as chloride ions, bromide ions and iodide ions, inorganic acids such as perchlorate ions, thiocyanate ions, tetrafluoroborate ions, nitrate ions, AsF 6 ⁇ and PF 6 ⁇
- Organic acid ions such as ions, stearyl sulfonate ions, octyl sulfonate ions, dodecylbenzene sulfonate ions, naphthalene sulfonate ions, dodecyl naphthalene sulfonate ions, 7,7,8,8-tetracyano-p-quinodimethane ions Etc. are exemplified.
- normal temperature molten salt may be used independently or may be used in mixture of 2 or more types.
- flame retardants and flame retardants include brominated epoxy compounds, phosphazene compounds, tetrabromobisphenol A, halides such as chlorinated paraffin, antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, phosphate esters, Examples thereof include polyphosphate and zinc borate.
- the negative electrode surface treatment agent include vinylene carbonate, fluoroethylene carbonate, and polyethylene glycol dimethyl ether.
- the positive electrode surface treatment agent include inorganic compounds such as carbon and metal oxides (such as MgO and ZrO 2 ), and organic compounds such as ortho-terphenyl.
- the overcharge inhibitor include biphenyl and 1- (p-tolyl) adamantane.
- an electrode and a coin battery were produced using the binder of the present invention, and the bending test and adhesion test were performed as the evaluation of the electrode, and the charge / discharge cycle characteristic performance was evaluated as the evaluation of the coin battery in the following experiment.
- Adhesion test (binding test) The adhesion test was performed by a cross cut test. Specifically, the electrode is cut to a width of 3 cm ⁇ length of 4 cm, and a grid pattern is cut with a cutter knife so that one side of one square is 1 mm, and from 25 squares of vertical 5 squares ⁇ horizontal 5 squares.
- a tape cello tape (registered trademark): manufactured by Nichiban) was applied to the grid, and the tape was peeled off at a stretch with the electrode fixed, the number of cells remaining without being peeled off from the electrode was measured. The test was performed 5 times, and the average value was obtained.
- Example of synthesis of binder composition [Exemplary Synthesis Example 1 of Binder Composition]
- A 40 parts by weight of polyethylene glycol monoacrylate (manufactured by NOF: Bremer AE-400), 1.3 parts by weight of acrylic acid, 3.7 parts by weight of methacrylic acid, 45 weights of methyl methacrylate Parts
- B 10 parts by weight of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-TMPT)
- C ammonium polyoxyalkylene alkenyl ether which is a reactive surfactant as an emulsifier (manufactured by Kao: Latemul PD-104) 20 wt% aqueous solution) as solids, 5 parts by weight of ion exchange water, 500 parts by weight of ion exchange water and 1 part by weight of potassium persulfate as a polymerization initiator, sufficiently e
- the average particle diameter of the obtained polymer was 0.102 ⁇ m.
- the average particle diameter of the obtained polymer was 0.096 ⁇ m.
- the average particle diameter of the obtained polymer was 0.122 ⁇ m.
- the average particle diameter of the obtained polymer was 0.101 ⁇ m.
- the binder composition was aggregated at the time when 3 hours had passed and integrated without becoming fine particles.
- the obtained binder composition had poor dispersibility with the positive electrode member (active material, conductive material, thickener), and a uniform electrode could not be formed.
- Example of electrode production Of the binder composition A obtained in Example Synthesis Example 1 of 90.6 parts by weight of nickel / manganese / lithium cobaltate (ternary system) as a positive electrode active material, 6.4 parts by weight of acetylene black as a conductive additive, Add 1 part by weight of solid and 2 parts by weight of sodium salt of carboxymethyl cellulose as a thickener, and add water as a solvent so that the solid content of the slurry is 35% by weight. To obtain a positive electrode slurry. The obtained positive electrode slurry was coated on a 20 ⁇ m thick aluminum current collector using a 65 ⁇ m gap blade coater, dried at 110 ° C. in a vacuum state for 12 hours or more, and then pressed with a roll press machine. A positive electrode of 15 ⁇ m was produced. The evaluation results of flexibility and binding property are shown in Example 1 of Table 1.
- Example 2 of electrode production A positive electrode was produced in the same manner as in Example 1 for producing electrodes except that the binder composition B obtained in Example 2 for binder synthesis was used. The thickness of the positive electrode obtained was 13 ⁇ m. The evaluation results of flexibility and binding property are shown in Example 2 of Table 1.
- Example 3 of electrode production A positive electrode was produced in the same manner as in Example 1 for producing electrodes except that the binder composition C obtained in Example 3 for binder synthesis was used. The thickness of the positive electrode obtained was 13 ⁇ m. The evaluation results of flexibility and binding property are shown in Example 3 of Table 1.
- Example 4 of electrode production A positive electrode was produced in the same manner as in Example 1 for producing electrodes except that the binder composition D obtained in Example 4 for binder synthesis was used. The thickness of the positive electrode obtained was 14 ⁇ m. The evaluation results of flexibility and binding property are shown in Example 4 of Table 1.
- Example 5 of electrode production A positive electrode was produced in the same manner as in Example 1 for electrode production except that the binder composition E obtained in Synthesis Example 5 for binder was used. The thickness of the obtained positive electrode was 15 ⁇ m. The evaluation results of flexibility and binding property are shown in Example 5 of Table 1.
- a positive electrode was produced in the same manner as in Example 1 for producing electrodes except that the binder composition F obtained in Comparative Synthesis Example 1 for binder was used.
- the thickness of the positive electrode obtained was 14 ⁇ m.
- the evaluation results of flexibility and binding property are shown in Comparative Example 1 in Table 1.
- a positive electrode was produced in the same manner as in Example 1 for producing electrodes except that the binder composition G obtained in Comparative Synthesis Example 2 for binder was used.
- the thickness of the obtained positive electrode was 15 ⁇ m.
- the evaluation results of flexibility and binding property are shown in Comparative Example 2 in Table 1.
- Example of battery production [Example of coin battery production 1]
- a positive electrode obtained in Example 1 of electrode fabrication, two 18 ⁇ m thick polypropylene / polyethylene / polypropylene porous membranes as separators, and a 300 ⁇ m thick metallic lithium foil as a counter electrode
- the laminated laminate is sufficiently impregnated with 1 mol / L lithium hexafluorophosphate ethylene carbonate and dimethyl carbonate solution (volume ratio 1: 1) as an electrolytic solution to produce a 2032 coin cell for testing. did.
- the evaluation results of the capacity retention rate after 100 cycles are shown in Example 1 of Table 1.
- Example of coin battery production 2 A coin battery was produced in the same manner as in the coin battery example 1 except that the positive electrode obtained in Example 2 of the electrode was used. The evaluation results of the capacity retention rate after 100 cycles are shown in Example 2 of Table 1.
- Example 3 of coin battery production A coin battery was produced in the same manner as in the coin battery production example 1 except that the positive electrode obtained in the electrode production example 3 was used. The evaluation results of the capacity retention rate after 100 cycles are shown in Example 3 of Table 1.
- Example of coin battery production 4 A coin battery was produced in the same manner as in the coin battery production example 1 except that the positive electrode obtained in the electrode production example 4 was used. The evaluation results of the capacity retention rate after 100 cycles are shown in Example 4 of Table 1.
- Example 5 of coin battery production A coin battery was made in the same manner as in the coin battery example 1 except that the positive electrode obtained in the electrode example 5 was used. The evaluation results of the capacity retention rate after 100 cycles are shown in Example 5 of Table 1.
- Comparative Example 1 of coin battery A coin battery was produced in the same manner as in the coin battery example 1 except that the positive electrode obtained in Comparative electrode production example 1 was used. The evaluation results of the capacity retention rate after 100 cycles are shown in Comparative Example 1 in Table 1.
- Comparative Example 2 of coin battery A coin battery was produced in the same manner as in the coin battery example 1 except that the positive electrode obtained in Comparative electrode production example 2 was used. The evaluation results of the capacity retention rate after 100 cycles are shown in Comparative Example 2 in Table 1.
- Comparative Example 3 of coin battery A coin battery was produced in the same manner as in the coin battery example 1 except that the positive electrode obtained in Comparative electrode production example 3 was used. The evaluation results of the capacity retention rate after 100 cycles are shown in Comparative Example 3 in Table 1.
- Table 1 shows examples and comparative examples.
- the battery binder (lithium secondary battery binder) of the present invention is a water system with high binding power, small environmental load, and from the viewpoint that the performance does not affect the temperature, the lithium ion secondary battery using this binder is It can be suitably used for small-sized batteries such as mobile phones, notebook PCs, camcorders and other electronic devices, as well as for large-sized lithium ion secondary batteries such as electric vehicles and hybrid electric vehicles, and storage batteries for household power storage. is there.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
リチウムイオン二次電池はエネルギー密度が高く、高電圧であるため、携帯電話やノートパソコン、カムコーダーなどの電子機器に用いられている。最近では環境保護への意識の高まりや関連法の整備により、電気自動車やハイブリッド電気自動車などの車載用途や家庭用電力貯蔵用の蓄電池としての応用も進んできている。
さらに、特許文献3および4では、芳香族ビニル、共役ジエン、(メタ)アクリル酸エステルおよびエチレン性不飽和カルボン酸からなる共重合体を含有するバインダー(特許文献3)、および2官能(メタ)アクリレートを含むポリマーを含有するバインダー(特許文献4)を提案している。
しかしながら、これらのバインダーを電極(正極および/または負極)に用いた場合、高温条件下において、充放電サイクルの容量低下が起こる。特に、正極に用いた場合、高電圧条件下で耐酸化性に問題があり、電池特性が悪くなることが懸念される。
[1]
(I)水酸基を有する(メタ)アクリレートモノマー(A)から誘導される構成単位と、
(II)多官能(メタ)アクリレートモノマー(B)から誘導される構成単位と、
(III)反応性界面活性剤(C)から誘導される構成単位と、
を含む重合体を含有することを特徴とする電池電極用バインダー。
[2]
水酸基を有する(メタ)アクリレートモノマー(A)の分子量が100~1000のアルキレングリコールモノ(メタ)アクリレートである[1]記載の電池電極用バインダー。
[3]
水酸基を有する(メタ)アクリレートモノマー(A)が、一般式:
( 式中、R1は水素または炭素数1~4の直鎖もしくは分岐のアルキル基であり、R2およびR3はそれぞれ水素、炭素数1~4の直鎖もしくは分岐のアルキル基、nは1~30の整数である。)
で示される化合物である請求項1または2に記載の電池電極用バインダー。
[4]
多官能(メタ)アクリレートモノマー(B)が2~5官能の(メタ)アクリレートである請求項[1]~[3]のいずれかに記載の電池電極用バインダー。
[5]
多官能(メタ)アクリレートモノマー(B)が、式:
R12は、5価以下の炭素数2~100の有機基であり、
mは5以下の整数である。)
で示される化合物である[1]~[4]のいずれかに記載の電池電極用バインダー。
[6]
反応性界面活性剤(C)がエチレン性不飽和二重結合および界面活性を示す基を有する化合物である[1]~[5]のいずれかに記載の電池電極用バインダー。
[7]
反応性界面活性剤(C)が反応性アニオン界面活性剤である[1]~[6]のいずれかに記載の電池電極用バインダー。
[8]
重合体が、
(IV)(メタ)アクリル酸エステルモノマーおよび/または有機酸ビニルエステルモノマー(D)から誘導される構成単位と、
(V)(メタ)アクリル酸モノマー(E)から誘導される構成単位
の一方または両方をさらに有する請求項[1]~[7]のいずれかに記載の電池電極用バインダー。
[9]
(メタ)アクリル酸エステルモノマー(D)が、式:
(式中、R21は水素またはメチル基であり、
R22は、炭素数1~50の炭化水素基である。)
で示される化合物であり、
有機酸ビニルエステルモノマー(D)が、式:
CH2=CH-OCOR23
(式中、R23は、炭素数1~50の炭化水素基である。)
で示される化合物であり、
(メタ)アクリル酸モノマー(E)が、式:
で示される化合物である[1]~[8]のいずれかに記載の電池電極用バインダー。
[10]
モノマー(A)~(E)から誘導される構造単位の量が、重合体に対して、
(A)10~90重量%、(B)1~70重量%、(C)0.01~25重量%、(D)0~70重量%および(E)0~70重量%である[1]~[9]のいずれかに記載の電池電極用バインダー。
[11]
電池が二次電池である[1]~[10]のいずれかに記載の電池電極用バインダー。
[12]
[1]~[11]のいずれかに記載のバインダーと活物質とを含有することを特徴とする電池用電極。
[13]
[12]記載の電極を有することを特徴とする電池。
本発明のバインダーは、屈曲性に優れる電極を提供する。
本発明のバインダーは、電解液への溶解が抑制されており、実質的に電解液に溶解しない。この非溶解性は、架橋剤成分に多官能(メタ)アクリレートモノマーから誘導される構成単位を用いることにより高度に架橋した構造であるためと考えられる。
本発明のバインダーは、乳化に反応性界面活性剤を使用しており、界面活性剤が重合体の一部となるため、分散溶媒の泡立ちが低減され、スラリー作製時の脱泡操作の簡略化を行うことができる。
本発明のバインダーは、分散性に優れる。
本発明は、高容量を有し、電池寿命が長い電池、特に二次電池を提供することができる。二次電池は充放電サイクル特性に優れている。特に、二次電池は、長期サイクル寿命と高温(例えば、60℃)でのサイクル充放電特性に優れている。
本発明の二次電池は、高電圧で使用でき、かつ優れた耐熱性を有する。
バインダーは、水系(媒体が水である。)であるので、環境への負荷が少なく、有機溶媒の回収装置を必要としない。
(I)水酸基を有する(メタ)アクリレートモノマー(A)から誘導される構成単位と、
(II)多官能(メタ)アクリレートモノマー(B)から誘導される構成単位と、
(III)反応性界面活性剤(C)から誘導される構成単位と
を含む重合体を含有することを特徴とする電池電極用バインダーである。
水酸基を有する(メタ)アクリレートモノマー(A)は、一般式:
( 式中、R1は水素または炭素数1~4の直鎖もしくは分岐のアルキル基であり、R2およびR3はそれぞれ水素、炭素数1~4の直鎖もしくは分岐のアルキル基、nは1~30の整数である。)
で示される化合物であることが好ましい。nは1~30の整数である。好ましくはnが2~25、より好ましくは4~20の整数である。
R12は、5価以下の炭素数2~100の有機基であり、
mは5以下の整数である。)
で示される化合物であることが好ましい。
好ましくは、R12は、2~5価の有機基であり、mは2~5の整数である。さらに好ましくは、R12は、3~5価、特に3~4価の有機基であり、mは3~5の整数、特に3~4の整数である。
R12において、炭化水素基は、直鎖または分岐の炭化水素基であるが、分岐の炭化水素基であることが好ましい。炭化水素基の炭素数は、2~100、例えば3~50、特に4~30である。
反応性アニオン界面活性剤としては、硫酸エステル型、スルホン酸型、カルボン酸型、リン酸エステル型のアルカリ金属塩、アルカリ土類金属塩、アルカノールアミン塩、アンモニウム塩等を挙げることができる。硫酸エステル型、リン酸エステル型、カルボン酸型が好ましく、硫酸エステル型が特に好ましい。
硫酸エステル型の具体例としては、ラテムルPD-104、105(花王社製)、アデカリアソープSR(アデカ社製)、アクアロンHS(第一工業製薬社製)、アクアロンKH(第一工業製薬社製)、エレミノールRS(三洋化成社製)、アントックスEMH等が挙げられる。
反応性ノニオン界面活性剤としては、ポリオキシアルキレンアルケニルエーテル、ポリオキシエチレンアルキルプロペニルフェニルエーテル、α-ヒドロ-ω-(1-アルコキシメチル-2-(2-プロペニルオキシ)エトキシ)-ポリ(オキシ-1,2-エタンジイル)等を挙げることができる。具体例としては、ラテムルPD-420、430、450(花王社製)、アデカリアソープER(アデカ社製)、アクアロンRN(第一工業製薬社製)等が挙げられる。
(I)水酸基を有する(メタ)アクリレートモノマー(A)から誘導される構成単位と
(II)多官能(メタ)アクリレートモノマー(B)から誘導される構成単位と
(III)反応性界面活性剤(C)から誘導される構成単位の他に、
(IV)(メタ)アクリル酸エステルモノマーおよび/または有機酸ビニルエステルモノマー(D)から誘導される構成単位と、
(V)(メタ)アクリル酸モノマー(E)から誘導される構成単位
の一方または両方を有していてもよい。
構成単位(A)+(B)+(C)
構成単位(A)+(B)+(C)+(D)
構成単位(A)+(B)+(C)+(E)
構成単位(A)+(B)+(C)+(D)+(E)
本発明において、モノマー(A)~(E)のそれぞれは、1種であってよくまたは2種以上を併用できる。モノマー(A)~(E)以外の他のモノマーを使用することが可能である。
(式中、R21は水素またはメチル基であり、
R22は、炭素数1~50の炭化水素基である。)
で示される化合物であることが好ましい。
R22は、一価の有機基であり、飽和または不飽和の脂肪族基(例えば、鎖状脂肪族基または環状脂肪族基)、芳香族基または芳香脂肪族基であってよい。R22は飽和の炭化水素基、特に飽和の脂肪族基であることが好ましい。R22基は、分岐または直鎖のアルキル基であることが特に好ましい。R22の炭素数は、1~50、例えば1~30、特に1~20、特別に1~10である。
CH2=CH-OCOR23
(式中、R23は、炭素数1~50の炭化水素基である。)
で示される化合物であることが好ましい。
R23は、一価の有機基であり、飽和または不飽和の脂肪族基(例えば、鎖状脂肪族基または環状脂肪族基)、芳香族基または芳香脂肪族基であってよい。R23は飽和の炭化水素基、特に飽和の脂肪族基であることが好ましい。R23基は、分岐または直鎖のアルキル基であることが特に好ましい。R23の炭素数は、1~50、例えば1~30、特に1~20である。
本発明において、使用モノマー(即ち、モノマー(A)、(B)、(C)、(D)および(E)ならびに他のモノマー)は、(メタ)アクリル基に含まれるエチレン性不飽和二重結合以外に、芳香族の炭素-炭素二重結合を含む炭素-炭素二重結合(および炭素-炭素三重結合)を有しないことが好ましい。
水酸基を有する(メタ)アクリレートモノマー(A)の構成単位の量100重量部に対して、
(B)0.5~100重量部、好ましくは1~80重量部、更に好ましくは2~70重量部、
(C)0.5~100重量部、好ましくは1~80重量部、更に好ましくは2~70重量部、
(D)0~500重量部、好ましくは1~400重量部、更に好ましくは2~300重量部、および
(E)0~100重量部、好ましくは0.5~80重量部、更に好ましくは1~50重量部
であってよい。
(A)10~90重量%、(B)1~70重量%、(C)0.01~25重量%、(D)0~70重量%および(E)0~70重量%であり、
好ましくは(A)20~80重量%、(B)2~50重量%、(C)0.05~20重量%、(D)0~60重量%および(E)0~60重量%であり、
更に好ましくは
(A)20~70重量%、(B)3~40重量%、(C)0.1~15重量%、(D)0~50重量%および(E)0~50重量%であってよい。
モノマー(D)およびモノマー(E)から誘導される構造単位の合計量の上限は、70重量%、例えば60重量%、特に50重量%であってよく、下限は、0重量%、例えば0.1重量%であってよい。
他の単量体の量は、重合体に対して、40重量%以下、例えば0~20重量%、特に0.1~15重量%であってよい。
本発明のバインダーを使用した電池電極用スラリーの調製方法としては特に限定されず、本発明のバインダー、活物質、導電助剤、水、必要に応じて増粘剤等を通常の攪拌機、分散機、混練機、遊星型ボールミル、ホモジナイザーなど用いて分散させればよい。分散の効率を上げるために材料に影響を与えない範囲で加温してもよい。
消泡剤としてはシリコーン系消泡剤、鉱油系消泡剤、ポリエーテル系消泡剤などがある。シリコーン系および鉱油系消泡剤が好ましい。
シリコーン系消泡剤としてはジメチルシリコーン系、メチルフェニルシリコーン系、メチルビニルシリコーン系消泡剤があり、好ましくはジメチルシリコーン系である。これらの消泡剤は、それぞれ単独で、または2種以上を混合して使用できる。
電池用の電極の作製方法は特に限定されず一般的な方法が用いられる。例えば、正極活物質あるいは負極活物質、導電助剤、バインダー、水、必要に応じて増粘剤などからなる電池電極用スラリーの調製液(塗工液)をドクターブレード法や、アプリケーター法、シルクスクリーン法などにより集電体表面上に適切な厚さに均一に塗布することより行われる。
以下の電池の製造法は、主として、リチウムイオン二次電池の製造方法である。
電池、特に二次電池の製造方法は特に限定されず、正極、負極、セパレータ、電解液、集電体で構成され、公知の方法にて製造される。例えば、コイン型の電池の場合、正極、セパレータ、負極を外装缶に挿入する。これに電解液を入れ含浸する。その後、封口体とタブ溶接などで接合して、封口体を封入し、かしめることで蓄電池が得られる。電池の形状は限定されないが、例としてはコイン型、円筒型、シート型などがあげられ、2個以上の電池を積層した構造でもよい。
作製した電極の評価としては屈曲試験と密着試験を行った。評価結果を表1にまとめて示した。
屈曲試験
屈曲試験はマンドレル屈曲試験にて行った。具体的には電極を幅3cm×長さ8cmに切り、長さ方向の中央(4cm部分)の基材側(電極表面が外側を向くように)に直径2mmのステンレス棒を支えにして180°折り曲げたときの折り曲げ部分の塗膜の状態を観察した。この方法で5回測定を行い、5回とも電極表面のひび割れまたは剥離や集電体からの剥がれが全く生じていない場合を○、1回でも1箇所以上のひび割れまたは剥がれが生じた場合を×と評価した。
密着試験はクロスカット試験にて行った。具体的には電極を幅3cm×長さ4cmに切り、1マスの1辺が1mmとなるように直角の格子パターン状にカッターナイフで切れ込みを入れ、縦5マス×横5マスの25マスからなる碁盤目にテープ(セロテープ(登録商標):ニチバン製)を貼り付け、電極を固定した状態でテープを一気に引き剥がしたとき、電極から剥がれずに残ったマスの数を計測した。試験は5回実施し、その平均値を求めた。
作製した電池の評価としては充放電装置を用いて充放電サイクル特性試験を行い、容量維持率を求めた。評価結果を表1にまとめて示した。
容量維持率
電気化学特性は(株)ナガノ製の充放電装置を用い、4.2Vを上限、2.5Vを下限とし、初回から3回目までは8時間で所定の充電および放電が行える試験条件(C/8)、4回目以降は1時間で所定の充電および放電が行える試験条件(1C)にて一定電流通電することにより電池の充放電サイクル特性を評価した。試験温度は60℃の環境とした。可逆容量は4サイクル目の放電容量の値を採用し、容量維持率は充放電を100サイクル行った後の放電容量と4サイクル目の放電容量の比で評価した。
[バインダー組成物の実施合成例1]
攪拌機付き反応容器に、(A)ポリエチレングリコールモノアクリレート(日油製:ブレンマーAE-400)40重量部、アクリル酸1.3重量部、メタアクリル酸3.7重量部、メタアクリル酸メチル45重量部、(B)トリメチロールプロパントリアクリレート(新中村化学製:A-TMPT)10重量部、乳化剤として反応性界面活性剤である(C)ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(花王製:ラテムルPD-104、20wt%水溶液)を固形分として5重量部、イオン交換水500重量部および重合開始剤として過硫酸カリウム1重量部を入れ、ホモジナイザーを用いて十分乳化させた後、窒素雰囲気下で60℃に加温し5時間重合し、その後、冷却した。冷却後、24%水酸化ナトリウム水溶液を用いて、重合液をpH8.1に調整してバインダー組成物A(重合転化率99%以上)(固形分濃度17wt%)を得た。得られた重合体の平均粒子径は0.102μmであった。
攪拌機付き反応容器に、(A)ポリプロピレングリコールモノアクリレート(日油製:ブレンマーAP-400)41重量部、アクリル酸1重量部、メタアクリル酸4重量部、メタアクリル酸メチル41部、(B)トリメチロールプロパントリアクリレート(新中村化学製:A-TMPT)13重量部、乳化剤として反応性界面活性剤である(C)ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(花王製:ラテムルPD-104、20wt%水溶液)を固形分として5重量部、イオン交換水500重量部および重合開始剤として過硫酸カリウム1重量部を入れ、ホモジナイザーを用いて十分乳化させた後、窒素雰囲気下で60℃に加温し5時間重合し、その後冷却した。冷却後、24%水酸化ナトリウム水溶液を用いて、重合液をpH8.2に調整し、バインダー組成物B(重合転化率99%以上)(固形分濃度17wt%)を得た。得られた重合体の平均粒子径は0.096μmであった。
攪拌機付き反応容器に、(A)ポリエチレングリコールモノアクリレート(日油製:ブレンマーAE-200)30重量部、アクリル酸2重量部、アクリル酸ブチル35重量部、メタアクリル酸メチル20重量部(B)トリメチロールプロパントリアクリレート(新中村化学製:A-TMPT)13重量部、乳化剤として反応性界面活性剤である(C)ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(花王製:ラテムルPD-104、20wt%水溶液)を固形分として3重量部およびポリオキシアルキレンアルケニルエーテル(花王製:ラテムルPD-450)を3重量部、イオン交換水150重量部および重合開始剤として過硫酸アンモニウム0.2重量部を入れ、ホモジナイザーを用いて十分乳化させた後、窒素雰囲気下で60℃に加温し5時間重合し、その後、冷却した。冷却後、24%水酸化ナトリウム水溶液を用いて、重合液をpH8.0に調整してバインダー組成物C(重合転化率99%以上)(固形分濃度41wt%)を得た。得られた重合体の平均粒子径は0.113μmであった。
攪拌機付き反応容器に、(A)ポリプロピレングリコールモノアクリレート(日油製:ブレンマーAP-400)45重量部、アクリル酸3重量部、アクリル酸-2-エチルヘキシル45重量部、(B)トリメチロールプロパントリアクリレート(新中村化学製:A-TMPT)7重量部、乳化剤として反応性界面活性剤である(C)ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(花王製:ラテムルPD-104、20wt%水溶液)を固形分として4重量部イオン交換水150重量部および重合開始剤として過硫酸カリウム0.3重量部を入れ、ホモジナイザーを用いて十分乳化させた後、窒素雰囲気下で60℃に加温し5時間重合し、その後、冷却した。冷却後、28%アンモニウム水溶液を用いて、重合液をpH8.0に調整してバインダー組成物D(重合転化率99%以上)(固形分濃度40wt%)を得た。得られた重合体の平均粒子径は0.122μmであった。
攪拌機付き反応容器に、(A)ポリエチレンリコールモノアクリレート(日油製:ブレンマーAE-200)43重量部、アクリル酸2重量部、酢酸ビニル30重量部、アクリル酸ブチル20重量部、(B)ポリエチレングリコールジアクリレート(日油製:ブレンマーADE-200)5重量部、乳化剤として反応性界面活性剤である(C)ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(花王製:ラテムルPD-104、20wt%水溶液)を固形分として3重量部およびポリオキシアルキレンアルケニルエーテル(花王製:ラテムルPD-420)を1重量部、イオン交換水150重量部および重合開始剤として過硫酸カリウム0.2重量部を入れ、ホモジナイザーを用いて十分乳化させた後、窒素雰囲気下で60℃に加温し5時間重合し、その後、冷却した。冷却後、10%水酸化ナトリウム水溶液を用いて、重合液をpH8.0に調整してバインダー組成物E(重合転化率99%以上)(固形分濃度40wt%)を得た。得られた重合体の平均粒子径は0.134μmであった。
攪拌機付き反応容器に、アクリル酸エチル20重量部、メタアクリル酸メチル60重量部、アクリル酸2重量部、メタアクリル酸3重量部、(B)ポリエチレングリコールジアクリレート(日油製:ブレンマーADE-200)15重量部、乳化剤として反応性界面活性剤である(C)ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(花王製:ラテムルPD-104、20wt%水溶液)を固形分として5重量部、イオン交換水500重量部および重合開始剤として過硫酸カリウム1重量部を入れ、ホモジナイザーを用いて十分乳化させた後、窒素雰囲気下で60℃に加温し5時間重合し、その後冷却した。冷却後、24%水酸化ナトリウム水溶液を用いて、重合液のpHを2.9から7.1に調整し、バインダー組成物F(重合転化率99%以上、固形分濃度17wt%)を得た。得られた重合体の平均粒子径は0.101μmであった。
攪拌機付き反応容器に、メタアクリル酸メチル45重量部、(A)ポリプロピレングリコールモノアクリレート(日油製:ブレンマーAP-400)50重量部、アクリル酸5重量部、乳化剤として反応性界面活性剤である(C)ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム(花王製:ラテムルPD-104、20wt%水溶液)を固形分として5重量部、イオン交換水500重量部および重合開始剤として過硫酸カリウム1重量部を入れ、ホモジナイザーを用いて十分乳化させた後、窒素雰囲気下で60℃に加温した。重合体は微粒子にならずに、撹拌を停止すると1時間程度で沈降した。撹拌しながら冷却後水酸化ナトリウム水溶液を用いて、重合液のpHを3.5から8.0に調整し、バインダー組成物G(重合転化率99%以上)(固形分濃度16wt%)を得た。
攪拌機付き反応容器に、(A)ポリプロピレングリコールモノアクリレート(日油製:ブレンマーAP-400)50重量部、メタクリル酸メチル35重量部、アクリル酸5重量部、(B)トリメチロールプロパントリアクリレート(新中村化学製:A-TMPT)10重量部、イオン交換水500重量部および重合開始剤として過硫酸カリウム1重量部を入れ、ホモジナイザーを用いて撹拌し、窒素雰囲気下で60℃に加温し重合を開始したが、3時間経過した時点で凝集し、微粒子とはならずに一体化したバインダー組成物を得た。
尚、得られたバインダー組成物は正極部材(活物質、導電材、増粘剤)との分散性が悪く、均一な電極を作成することができなった。
[電極の実施作製例1]
正極活物質としてニッケル/マンガン/コバルト酸リチウム(3元系)90.6重量部に、導電助剤としてアセチレンブラック6.4重量部、バインダーの実施合成例1で得られたバインダー組成物Aの固形分として1重量部および増粘剤としてカルボキシメチルセルロースのナトリウム塩2重量部を加え、さらにスラリーの固形分濃度が35重量%となるように溶媒となる水を加えて遊星型ミルを用いて十分に混合して正極用スラリーを得た。
得られた正極スラリーを厚さ20μmのアルミ集電体上に65μmギャップのブレードコーターを用いて塗布し、110℃真空状態で12時間以上乾繰後、ロールプレス機にてプレスを行い、厚さ15μmの正極を作製した。屈曲性および結着性の評価結果を表1の実施例1に示す。
バインダーの実施合成例2で得られたバインダー組成物Bを使用した以外は、電極の実施作製例1と同様にして正極を作製した。得られた正極の厚みは13μmであった。屈曲性および結着性の評価結果を表1の実施例2に示す。
バインダーの実施合成例3で得られたバインダー組成物Cを使用した以外は、電極の実施作製例1と同様にして正極を作製した。得られた正極の厚みは13μmであった。屈曲性および結着性の評価結果を表1の実施例3に示す。
バインダーの実施合成例4で得られたバインダー組成物Dを使用した以外は、電極の実施作製例1と同様にして正極を作製した。得られた正極の厚みは14μmであった。屈曲性および結着性の評価結果を表1の実施例4に示す。
バインダーの実施合成例5で得られたバインダー組成物Eを使用した以外は、電極の実施作製例1と同様にして正極を作製した。得られた正極の厚みは15μmであった。屈曲性および結着性の評価結果を表1の実施例5に示す。
バインダーの比較合成例1で得られたバインダー組成物Fを使用した以外は、電極の実施作製例1と同様にして正極を作製した。得られた正極の厚みは14μmであった。屈曲性および結着性の評価結果を表1の比較例1に示す。
バインダーの比較合成例2で得られたバインダー組成物Gを使用した以外は、電極の実施作製例1と同様にして正極を作製した。得られた正極の厚みは15μmであった。屈曲性および結着性の評価結果を表1の比較例2に示す。
正極活物質としてニッケル/マンガン/コバルト酸リチウム(3元系)88.7重量部に、導電助剤としてアセチレンブラック6.3重量部、バインダーとしてポリフッ化ビニリデン(PVDF、固形分濃度12wt%のN-メチル-2-ピロリドン溶液)を固形分として5重量部を加え、さらにスラリーの固形分濃度が40%となるように溶媒としてN-メチル-2-ピロリドンを加えて遊星型ミルを用いて十分に混合して正極用スラリー溶液を得た。
このようにして得られたスラリー溶液を使用した以外は、電極の作製例1と同様にして正極を作製した。得られた正極の厚みは17μmであった。屈曲性および結着性の評価結果を表1の比較例3に示す。
[コイン電池の実施製造例1]
アルゴンガスで置換されたグローブボックス内において、電極の実施作製例1で得た正極、セパレータとして厚み18μmのポリプロピレン/ポリエチレン/ポリプロピレン多孔質膜を2枚、更に対極として厚さ300μmの金属リチウム箔を貼り合わせた積層物に、電解液として1mol/Lの6フッ化リン酸リチウムのエチレンカーボネートとジメチルカーボネート溶液(体積比1:1)を十分に含浸させてかしめ、試験用2032型コイン電池を製造した。100サイクル後の容量維持率の評価結果を表1の実施例1に示す。
電極の実施作製例2で得た正極を用いた以外は、コイン電池の実施製造例1と同様にしてコイン電池を作製した。100サイクル後の容量維持率の評価結果を表1の実施例2に示す。
電極の実施作製例3で得た正極を用いた以外は、コイン電池の実施製造例1と同様にしてコイン電池を作製した。100サイクル後の容量維持率の評価結果を表1の実施例3に示す。
電極の実施作製例4で得た正極を用いた以外は、コイン電池の実施製造例1と同様にしてコイン電池を作製した。100サイクル後の容量維持率の評価結果を表1の実施例4に示す。
電極の実施作製例5で得た正極を用いた以外は、コイン電池の実施製造例1と同様にしてコイン電池を作製した。100サイクル後の容量維持率の評価結果を表1の実施例5に示す。
電極の比較作製例1で得た正極を用いた以外は、コイン電池の実施製造例1と同様にしてコイン電池を作製した。100サイクル後の容量維持率の評価結果を表1の比較例1に示す。
電極の比較作製例2で得た正極を用いた以外は、コイン電池の実施製造例1と同様にしてコイン電池を作製した。100サイクル後の容量維持率の評価結果を表1の比較例2に示す。
電極の比較作製例3で得た正極を用いた以外は、コイン電池の実施製造例1と同様にしてコイン電池を作製した。100サイクル後の容量維持率の評価結果を表1の比較例3に示す。
Claims (13)
- (I)水酸基を有する(メタ)アクリレートモノマー(A)から誘導される構成単位と、
(II)多官能(メタ)アクリレートモノマー(B)から誘導される構成単位と、
(III)反応性界面活性剤(C)から誘導される構成単位と、
を含む重合体を含有することを特徴とする電池電極用バインダー。 - 水酸基を有する(メタ)アクリレートモノマー(A)の分子量が100~1000のアルキレングリコールモノ(メタ)アクリレートである請求項1記載の電池電極用バインダー。
- 多官能(メタ)アクリレートモノマー(B)が2~5官能の(メタ)アクリレートである請求項1~3のいずれかに記載の電池電極用バインダー。
- 反応性界面活性剤(C)がエチレン性不飽和二重結合および界面活性を示す基を有する化合物である請求項1~5のいずれかに記載の電池電極用バインダー。
- 反応性界面活性剤(C)が反応性アニオン界面活性剤である請求項1~6のいずれかに記載の電池電極用バインダー。
- 重合体が、
(IV)(メタ)アクリル酸エステルモノマーおよび/または有機酸ビニルエステルモノマー(D)から誘導される構成単位と、
(V)(メタ)アクリル酸モノマー(E)から誘導される構成単位
の一方または両方をさらに有する請求項1~7のいずれかに記載の電池電極用バインダー。 - モノマー(A)~(E)から誘導される構造単位の量が、重合体に対して、
(A)10~90重量%、(B)1~70重量%、(C)0.01~25重量%、(D)0~70重量%および(E)0~70重量%である請求項1~9のいずれかに記載の電池電極用バインダー。 - 電池が二次電池である請求項1~10のいずれかに記載の電池電極用バインダー。
- 請求項1~11のいずれかに記載のバインダーと活物質とを含有することを特徴とする電池用電極。
- 請求項12に記載の電極を有することを特徴とする電池。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15758935.9A EP3116054A4 (en) | 2014-03-04 | 2015-03-03 | Binder for battery electrodes, and electrode and battery using same |
CN201580011167.0A CN106063005B (zh) | 2014-03-04 | 2015-03-03 | 电池电极用粘合剂、及使用了该粘合剂的电极和电池 |
KR1020187031530A KR20180121693A (ko) | 2014-03-04 | 2015-03-03 | 전지 전극용 바인더, 및 그것을 사용한 전극 그리고 전지 |
KR1020167021915A KR20160129002A (ko) | 2014-03-04 | 2015-03-03 | 전지 전극용 바인더, 및 그것을 사용한 전극 그리고 전지 |
JP2016506512A JP6341271B2 (ja) | 2014-03-04 | 2015-03-03 | 電池電極用バインダー、およびそれを用いた電極ならびに電池 |
US15/122,673 US10483545B2 (en) | 2014-03-04 | 2015-03-03 | Binder for battery electrodes, and electrode and battery using same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-041435 | 2014-03-04 | ||
JP2014041435 | 2014-03-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015133492A1 true WO2015133492A1 (ja) | 2015-09-11 |
Family
ID=54055298
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/056250 WO2015133492A1 (ja) | 2014-03-04 | 2015-03-03 | 電池電極用バインダー、およびそれを用いた電極ならびに電池 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10483545B2 (ja) |
EP (1) | EP3116054A4 (ja) |
JP (1) | JP6341271B2 (ja) |
KR (2) | KR20180121693A (ja) |
CN (1) | CN106063005B (ja) |
WO (1) | WO2015133492A1 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016199653A1 (ja) * | 2015-06-12 | 2016-12-15 | 昭和電工株式会社 | 非水系電池電極用バインダー用組成物、非水系電池電極用バインダー、非水系電池電極用組成物、非水系電池電極、及び非水系電池 |
JP2017069006A (ja) * | 2015-09-30 | 2017-04-06 | 株式会社大阪ソーダ | 電池電極用バインダー組成物およびその製造方法 |
JP2017103056A (ja) * | 2015-11-30 | 2017-06-08 | 日本ゼオン株式会社 | 非水系二次電池機能層用組成物、非水系二次電池機能層用組成物の製造方法、非水系二次電池用機能層及び非水系二次電池 |
JP2017168213A (ja) * | 2016-03-14 | 2017-09-21 | 東洋インキScホールディングス株式会社 | 蓄電デバイス用樹脂微粒子、蓄電デバイス電極、蓄電デバイス。 |
JP2018101519A (ja) * | 2016-12-20 | 2018-06-28 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | 二次電池用バインダ、二次電池用バインダ樹脂組成物、二次電池用電極、および二次電池 |
WO2018207828A1 (ja) * | 2017-05-10 | 2018-11-15 | 東亞合成株式会社 | 硬化型組成物 |
WO2019131710A1 (ja) * | 2017-12-26 | 2019-07-04 | 昭和電工株式会社 | 非水系電池電極用バインダー、非水系電池電極用スラリー、非水系電池電極、及び非水系電池 |
CN110139881A (zh) * | 2017-02-15 | 2019-08-16 | 株式会社大阪曹達 | 电极用粘结剂 |
WO2021044968A1 (ja) * | 2019-09-05 | 2021-03-11 | 昭和電工株式会社 | 電極バインダー用共重合体及びリチウムイオン二次電池 |
JP7518369B2 (ja) | 2020-09-03 | 2024-07-18 | 藤倉化成株式会社 | 凹形状樹脂微粒子の製造方法 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10003077B2 (en) | 2013-10-29 | 2018-06-19 | Osaka Soda Co., Ltd. | Battery electrode binder and battery and electrode using same |
EP3116054A4 (en) * | 2014-03-04 | 2017-10-11 | Osaka Soda Co. Ltd. | Binder for battery electrodes, and electrode and battery using same |
CN107078276A (zh) * | 2014-10-27 | 2017-08-18 | 日立化成株式会社 | 锂离子电池 |
WO2018021552A1 (ja) * | 2016-07-29 | 2018-02-01 | 花王株式会社 | 蓄電デバイス電極用樹脂組成物 |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
CN106833448B (zh) * | 2017-02-08 | 2019-02-15 | 北京蓝海黑石科技有限公司 | 一种锂离子电池正极水性粘合剂及其制备方法 |
CN107732156A (zh) * | 2017-11-28 | 2018-02-23 | 安徽零度新能源科技有限公司 | 一种提高锂电池负极低温性能的加工方法 |
JP2020057579A (ja) * | 2017-12-26 | 2020-04-09 | 株式会社大阪ソーダ | 負極、及び蓄電デバイス |
US11699791B2 (en) * | 2019-08-16 | 2023-07-11 | Sk On Co., Ltd. | Binder for secondary battery and secondary battery including the same |
CN110982008B (zh) * | 2019-12-30 | 2022-01-07 | 浙江研一新能源科技有限公司 | 锂离子电池负极水性粘结剂 |
CN111057184B (zh) * | 2019-12-30 | 2022-02-25 | 宣城研一新能源科技有限公司 | 负极极片水性粘结剂的制备方法 |
CN114335542B (zh) * | 2021-12-31 | 2024-06-14 | 湖南高瑞电源材料有限公司 | 一种改善锂电池负极片开裂的添加剂及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006519883A (ja) * | 2003-06-03 | 2006-08-31 | エルジー・ケム・リミテッド | 分散剤が化学結合された電極用複合バインダー重合体 |
JP2012185947A (ja) * | 2011-03-04 | 2012-09-27 | Toyo Ink Sc Holdings Co Ltd | 非水系二次電池電極用バインダー組成物 |
JP2014029850A (ja) * | 2012-06-28 | 2014-02-13 | Nippon Zeon Co Ltd | リチウムイオン二次電池負極用スラリー組成物、二次電池用負極および二次電池 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3721727B2 (ja) | 1997-07-04 | 2005-11-30 | Jsr株式会社 | 電池電極用バインダー |
JP4325061B2 (ja) | 2000-03-09 | 2009-09-02 | 日本ゼオン株式会社 | リチウムイオン二次電池電極用バインダーおよびその利用 |
JP5077510B2 (ja) * | 2005-03-15 | 2012-11-21 | Jsr株式会社 | 二次電池負極用バインダー組成物、二次電池負極用スラリー、及び二次電池負極 |
JP2007013440A (ja) * | 2005-06-29 | 2007-01-18 | Toshiba Corp | メディア鍵生成方法、メディア鍵生成装置、再生装置、及び記録再生装置 |
JP4380608B2 (ja) | 2005-08-26 | 2009-12-09 | 日本ゼオン株式会社 | 有機溶媒系バインダー組成物、電極、および電池 |
KR101182128B1 (ko) * | 2010-07-22 | 2012-09-12 | 주식회사 엘지화학 | 접착력이 우수한 이차전지용 바인더 |
US8526133B2 (en) * | 2011-07-19 | 2013-09-03 | Lsi Corporation | Systems and methods for user data based fly height calculation |
EP2829184A4 (en) * | 2012-03-30 | 2015-12-30 | Japan Tobacco Inc | CARBON HEAT SOURCE AND AROMA INHALATION TOOL |
JP5447720B1 (ja) * | 2012-05-31 | 2014-03-19 | ダイソー株式会社 | 電池電極用バインダー、およびそれを用いた電極ならびに電池 |
EP3116054A4 (en) * | 2014-03-04 | 2017-10-11 | Osaka Soda Co. Ltd. | Binder for battery electrodes, and electrode and battery using same |
EP3352265A4 (en) * | 2015-09-14 | 2019-04-03 | Osaka Soda Co., Ltd. | POSITIVE ELECTRODE MATERIAL FOR SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE |
KR20180051498A (ko) * | 2015-09-14 | 2018-05-16 | 가부시키가이샤 오사카소다 | 비수전해질 이차전지용 양극재료 |
EP3396749A4 (en) * | 2015-12-21 | 2019-05-01 | Osaka Soda Co., Ltd. | BINDER FOR BATTERY ELECTRODE, ELECTRODE AND BATTERY |
-
2015
- 2015-03-03 EP EP15758935.9A patent/EP3116054A4/en not_active Withdrawn
- 2015-03-03 CN CN201580011167.0A patent/CN106063005B/zh active Active
- 2015-03-03 KR KR1020187031530A patent/KR20180121693A/ko not_active Application Discontinuation
- 2015-03-03 JP JP2016506512A patent/JP6341271B2/ja active Active
- 2015-03-03 KR KR1020167021915A patent/KR20160129002A/ko active Application Filing
- 2015-03-03 US US15/122,673 patent/US10483545B2/en active Active
- 2015-03-03 WO PCT/JP2015/056250 patent/WO2015133492A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006519883A (ja) * | 2003-06-03 | 2006-08-31 | エルジー・ケム・リミテッド | 分散剤が化学結合された電極用複合バインダー重合体 |
JP2012185947A (ja) * | 2011-03-04 | 2012-09-27 | Toyo Ink Sc Holdings Co Ltd | 非水系二次電池電極用バインダー組成物 |
JP2014029850A (ja) * | 2012-06-28 | 2014-02-13 | Nippon Zeon Co Ltd | リチウムイオン二次電池負極用スラリー組成物、二次電池用負極および二次電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3116054A4 * |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10957909B2 (en) | 2015-06-12 | 2021-03-23 | Showa Denko K.K. | Composition for binder for non-aqueous cell electrode, binder for non-aqueous cell electrode, composition for non-aqueous cell electrode, non-aqueous cell electrode, and non-aqueous cell |
JPWO2016199653A1 (ja) * | 2015-06-12 | 2017-12-07 | 昭和電工株式会社 | 非水系電池電極用バインダー用組成物、非水系電池電極用バインダー、非水系電池電極用組成物、非水系電池電極、及び非水系電池 |
WO2016199653A1 (ja) * | 2015-06-12 | 2016-12-15 | 昭和電工株式会社 | 非水系電池電極用バインダー用組成物、非水系電池電極用バインダー、非水系電池電極用組成物、非水系電池電極、及び非水系電池 |
JP2017069006A (ja) * | 2015-09-30 | 2017-04-06 | 株式会社大阪ソーダ | 電池電極用バインダー組成物およびその製造方法 |
JP2017103056A (ja) * | 2015-11-30 | 2017-06-08 | 日本ゼオン株式会社 | 非水系二次電池機能層用組成物、非水系二次電池機能層用組成物の製造方法、非水系二次電池用機能層及び非水系二次電池 |
JP2017168213A (ja) * | 2016-03-14 | 2017-09-21 | 東洋インキScホールディングス株式会社 | 蓄電デバイス用樹脂微粒子、蓄電デバイス電極、蓄電デバイス。 |
JP2018101519A (ja) * | 2016-12-20 | 2018-06-28 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | 二次電池用バインダ、二次電池用バインダ樹脂組成物、二次電池用電極、および二次電池 |
US11005102B2 (en) | 2016-12-20 | 2021-05-11 | Samsung Sdi Co., Ltd. | Binder for secondary battery, binder resin composition for secondary battery, electrode for secondary battery, and secondary battery |
CN110139881B (zh) * | 2017-02-15 | 2022-09-09 | 株式会社大阪曹達 | 电极用粘结剂 |
CN110139881A (zh) * | 2017-02-15 | 2019-08-16 | 株式会社大阪曹達 | 电极用粘结剂 |
JPWO2018207828A1 (ja) * | 2017-05-10 | 2020-03-12 | 東亞合成株式会社 | 硬化型組成物 |
WO2018207828A1 (ja) * | 2017-05-10 | 2018-11-15 | 東亞合成株式会社 | 硬化型組成物 |
JP7255480B2 (ja) | 2017-05-10 | 2023-04-11 | 東亞合成株式会社 | 硬化型組成物 |
WO2019131710A1 (ja) * | 2017-12-26 | 2019-07-04 | 昭和電工株式会社 | 非水系電池電極用バインダー、非水系電池電極用スラリー、非水系電池電極、及び非水系電池 |
US11764359B2 (en) | 2017-12-26 | 2023-09-19 | Resonac Corporation | Binder including copolymer of styrene, (meth)acrylate, and surfactant having unsaturated bond, slurry having the same, nonaqueous battery electrode using the same, and nonaqueous battery using the same |
WO2021044968A1 (ja) * | 2019-09-05 | 2021-03-11 | 昭和電工株式会社 | 電極バインダー用共重合体及びリチウムイオン二次電池 |
JP6890736B1 (ja) * | 2019-09-05 | 2021-06-18 | 昭和電工株式会社 | 電極バインダー用共重合体及びリチウムイオン二次電池 |
CN114080704A (zh) * | 2019-09-05 | 2022-02-22 | 昭和电工株式会社 | 电极粘合剂用共聚物以及锂离子二次电池 |
CN114080704B (zh) * | 2019-09-05 | 2023-01-13 | 昭和电工株式会社 | 电极粘合剂用共聚物以及锂离子二次电池 |
TWI838574B (zh) * | 2019-09-05 | 2024-04-11 | 日商力森諾科股份有限公司 | 電極黏合劑用共聚物及鋰離子二次電池 |
JP7518369B2 (ja) | 2020-09-03 | 2024-07-18 | 藤倉化成株式会社 | 凹形状樹脂微粒子の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP3116054A4 (en) | 2017-10-11 |
CN106063005B (zh) | 2020-11-17 |
EP3116054A1 (en) | 2017-01-11 |
US20170069913A1 (en) | 2017-03-09 |
JP6341271B2 (ja) | 2018-06-13 |
CN106063005A (zh) | 2016-10-26 |
US10483545B2 (en) | 2019-11-19 |
KR20160129002A (ko) | 2016-11-08 |
JPWO2015133492A1 (ja) | 2017-04-06 |
KR20180121693A (ko) | 2018-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6341271B2 (ja) | 電池電極用バインダー、およびそれを用いた電極ならびに電池 | |
JP5447720B1 (ja) | 電池電極用バインダー、およびそれを用いた電極ならびに電池 | |
JP6269510B2 (ja) | 電池電極用バインダー、およびそれを用いた電極ならびに電池 | |
JP6164303B2 (ja) | 電池電極用バインダー、およびそれを用いた電極ならびに電池 | |
JP6268988B2 (ja) | 電池電極用バインダー、およびそれを用いた電極ならびに電池 | |
JP6300078B2 (ja) | 電池電極用スラリー組成物、およびそれを用いた電極ならびに電池 | |
WO2017110901A1 (ja) | 電池電極用バインダー、電極、及び電池 | |
JP6874682B2 (ja) | 非水電解質二次電池用の正極材料 | |
JP2016046231A (ja) | 電池正極用バインダー組成物、およびそれを用いた電極ならびに電池 | |
JP6395107B2 (ja) | 電池電極用バインダー組成物、およびそれを用いた電極ならびに電池 | |
JP2016192267A (ja) | 電池電極用バインダー、およびそれを用いた電極ならびに電池 | |
CN110139881B (zh) | 电极用粘结剂 | |
JPWO2019017479A1 (ja) | 電極用バインダー、電極用バインダー組成物、電極材料、電極、及び蓄電デバイス | |
JP2017117522A (ja) | 電池電極用バインダー、およびそれを用いた電極ならびに電池 | |
JP7088171B2 (ja) | 電極用バインダー、電極材料、電極、及び蓄電デバイス | |
JP2017069006A (ja) | 電池電極用バインダー組成物およびその製造方法 | |
JP2017091789A (ja) | 正極、二次電池およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15758935 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016506512 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167021915 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15122673 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015758935 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015758935 Country of ref document: EP |