WO2013077212A1 - 蓄電デバイス用バインダー組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極、保護膜形成用スラリー、保護膜、および蓄電デバイス - Google Patents
蓄電デバイス用バインダー組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極、保護膜形成用スラリー、保護膜、および蓄電デバイス Download PDFInfo
- Publication number
- WO2013077212A1 WO2013077212A1 PCT/JP2012/079271 JP2012079271W WO2013077212A1 WO 2013077212 A1 WO2013077212 A1 WO 2013077212A1 JP 2012079271 W JP2012079271 W JP 2012079271W WO 2013077212 A1 WO2013077212 A1 WO 2013077212A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- storage device
- electricity storage
- electrode
- slurry
- protective film
- Prior art date
Links
- 238000003860 storage Methods 0.000 title claims abstract description 328
- 230000005611 electricity Effects 0.000 title claims abstract description 260
- 239000000203 mixture Substances 0.000 title claims abstract description 135
- 239000011230 binding agent Substances 0.000 title claims abstract description 122
- 230000001681 protective effect Effects 0.000 title claims description 124
- 239000002002 slurry Substances 0.000 title claims description 123
- 239000002245 particle Substances 0.000 claims abstract description 408
- 229920000642 polymer Polymers 0.000 claims abstract description 255
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011737 fluorine Substances 0.000 claims abstract description 21
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 12
- 239000011149 active material Substances 0.000 claims description 77
- 239000010954 inorganic particle Substances 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 26
- 239000011267 electrode slurry Substances 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 27
- 239000010408 film Substances 0.000 description 118
- -1 olefin compound Chemical class 0.000 description 56
- 238000000034 method Methods 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 38
- 239000007787 solid Substances 0.000 description 35
- 239000006185 dispersion Substances 0.000 description 33
- 238000002360 preparation method Methods 0.000 description 33
- 238000004519 manufacturing process Methods 0.000 description 28
- 239000000178 monomer Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 27
- 238000011156 evaluation Methods 0.000 description 26
- 239000002562 thickening agent Substances 0.000 description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 24
- 229910001416 lithium ion Inorganic materials 0.000 description 24
- 239000012736 aqueous medium Substances 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 22
- 238000009826 distribution Methods 0.000 description 22
- 239000008151 electrolyte solution Substances 0.000 description 22
- 210000004027 cell Anatomy 0.000 description 20
- 238000005259 measurement Methods 0.000 description 19
- 239000007774 positive electrode material Substances 0.000 description 19
- 239000007773 negative electrode material Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- 239000002609 medium Substances 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 15
- 238000007599 discharging Methods 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000011164 primary particle Substances 0.000 description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 8
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 7
- 210000001787 dendrite Anatomy 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000004962 Polyamide-imide Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 238000007606 doctor blade method Methods 0.000 description 6
- 230000001788 irregular Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229920002312 polyamide-imide Polymers 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000010450 olivine Substances 0.000 description 5
- 229910052609 olivine Inorganic materials 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 239000011883 electrode binding agent Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000002641 lithium Chemical group 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002019 disulfides Chemical class 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
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 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
- 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
- HVYJSOSGTDINLW-UHFFFAOYSA-N 2-[dimethyl(octadecyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- DFWPREUTILPHQS-UHFFFAOYSA-N 2-amino-2-cyanopropanamide Chemical compound N#CC(N)(C)C(N)=O DFWPREUTILPHQS-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- RZRUOQGLPXQNBX-UHFFFAOYSA-N 2-methyl-n-[3-(methylamino)propyl]prop-2-enamide Chemical compound CNCCCNC(=O)C(C)=C RZRUOQGLPXQNBX-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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- AEDQNOLIADXSBB-UHFFFAOYSA-N 3-(dodecylazaniumyl)propanoate Chemical compound CCCCCCCCCCCCNCCC(O)=O AEDQNOLIADXSBB-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- RINDUYMVZWQJDB-UHFFFAOYSA-N 4-amino-2-methylidenebutanamide Chemical compound NCCC(=C)C(N)=O RINDUYMVZWQJDB-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- XQFRJNBWHJMXHO-RRKCRQDMSA-N IDUR Chemical compound C1[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)NC(=O)C(I)=C1 XQFRJNBWHJMXHO-RRKCRQDMSA-N 0.000 description 1
- 229920006369 KF polymer Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- CQLZEWXXRJJDKG-UHFFFAOYSA-N azanium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecanoate Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CQLZEWXXRJJDKG-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000002180 crystalline carbon material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 229960002377 dixanthogen Drugs 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000002593 electrical impedance tomography Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000005290 ethynyloxy group Chemical group C(#C)O* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- HKTGZPQHFCONFD-UHFFFAOYSA-N n-[(dimethylamino)methyl]-2-methylprop-2-enamide Chemical compound CN(C)CNC(=O)C(C)=C HKTGZPQHFCONFD-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000002081 peroxide group Chemical group 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
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 229930193351 phorone Natural products 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 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
- 150000004992 toluidines Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention includes a power storage device binder composition, a power storage device electrode slurry containing the binder composition and an active material, a power storage device electrode formed by applying the slurry to a current collector, and the electrode
- the present invention relates to a power storage device, a slurry for forming a protective film containing the binder composition and inorganic particles, a protective film formed from the slurry, and a power storage device including the protective film.
- lithium ion batteries and lithium ion capacitors are expected as power storage devices having high voltage and high energy density.
- An electricity storage device electrode used for such an electricity storage device is usually produced by applying and drying a mixture of active material particles and polymer particles functioning as an electrode binder on the surface of the current collector.
- the properties required for the polymer particles used as the binder for the electrode include the bonding between the active material particles and the binding ability between the active material particles and the current collector, the abrasion resistance in the step of winding the electrode, There is a powder fall resistance in which fine powder of the active material is not generated from the electrode composition layer (hereinafter also referred to as “active material layer”) applied by cutting or the like.
- the quality of the active material particles is substantially proportional to the ability to bind the active material particles, the binding ability between the active material particles and the current collector, and the powder-off resistance. . Therefore, in the present specification, these may be collectively expressed below using the term “adhesion”.
- the polymer used as the binder for the electrode is advantageously a fluorine-containing organic polymer having excellent oxidation resistance such as polyvinylidene fluoride.
- the negative electrode it is advantageous to use a (meth) acrylic acid-based polymer that is inferior in oxidation resistance but excellent in adhesion.
- various techniques for further improving adhesion while maintaining oxidation resistance have been proposed.
- Japanese Patent Application Laid-Open No. 2011-3529 proposes a technique for achieving both the oxidation resistance and adhesion of a negative electrode binder by using polyvinylidene fluoride and a rubber-based polymer in combination.
- Japanese Patent Application Laid-Open No. 2010-55847 improves the adhesion by dissolving polyvinylidene fluoride in a specific organic solvent, applying it on the surface of the current collector, and then removing the solvent at a low temperature. Techniques to do so have been proposed.
- 2002-42819 proposes a technique for improving adhesion by applying an electrode binder having a structure having a side chain having a fluorine atom to the main chain made of a vinylidene fluoride copolymer.
- an electrode binder having a structure having a side chain having a fluorine atom to the main chain made of a vinylidene fluoride copolymer.
- Japanese Patent Laid-Open No. 2000-299109 discloses a technique for improving the above characteristics by controlling the binder composition
- Japanese Patent Laid-Open Nos. 2010-205722 and 2010-3703 have an epoxy group or a hydroxyl group. Techniques for improving the above characteristics using a binder have been studied.
- a porous layer containing a resin binder containing polyamide, polyimide and polyamideimide is formed on a porous separator substrate.
- a technique for improving the battery characteristics by forming them has been studied.
- Japanese Patent Application Laid-Open No. 2009-54455 improves battery characteristics by forming a porous protective film containing a binder containing a fluorine-based resin and a rubber-based resin on at least one surface of a positive electrode and a negative electrode.
- the binder composition described in JP 2000-299109 A, JP 2010-205722 A, and JP 2010-3703 A improves the adhesion, but the binder itself adhering to the active material itself. Becomes a resistance component of the electrode, and it has been difficult to maintain good charge / discharge characteristics over a long period of time.
- some embodiments according to the present invention provide a binder composition for an electricity storage device capable of producing an electricity storage device having excellent adhesion and excellent charge / discharge characteristics by solving at least a part of the above problems. To do.
- some aspects of the present invention provide a protective film that solves at least a part of the above-described problems, and is excellent in electrolyte permeability and liquid retention, and can suppress an increase in internal resistance of the electricity storage device,
- the present invention provides a slurry for producing the protective film and an electricity storage device provided with the protective film.
- the present invention has been made to solve at least a part of the above-described problems, and can be realized as the following aspects or application examples.
- One aspect of the binder composition for an electricity storage device is: An electricity storage device comprising polymer particles (A) containing a repeating unit (a) derived from a fluorine-containing compound and a repeating unit (b) derived from a polyfunctional (meth) acrylate, and a liquid medium (B)
- A polymer particles
- DSC differential scanning calorimetry
- the quantitative ratio of the repeating unit (a) to the repeating unit (b) may be in the range of 2: 1 to 10: 1 on a mass basis.
- the number average particle diameter of the polymer particles (A) may be in the range of 50 to 400 nm.
- the ratio (Rmax / Rmin) of the major axis (Rmax) to the minor axis (Rmin) of the polymer particles (A) may be in the range of 1.1 to 1.5.
- the polymer particle (A) further includes a repeating unit (c) derived from an unsaturated carboxylic acid, and the repeating unit derived from the fluorine-containing compound (a) with respect to 100 parts by mass of the polymer particle (A) (a ) 5 to 50 parts by mass and 1 to 10 parts by mass of the repeating unit (c) derived from the unsaturated carboxylic acid.
- the binder composition for an electricity storage device according to any one of Application Example 1 to Application Example 5, It can be used for the purpose of producing a positive electrode of an electricity storage device.
- One aspect of the slurry for the electricity storage device electrode according to the present invention is: It contains the binder composition for electrical storage devices of any one example of the application example 1 thru
- One aspect of the electricity storage device electrode according to the present invention is: It is characterized by comprising: a current collector; and an active material layer produced by applying and drying the electricity storage device electrode slurry of Application Example 7 on the surface of the current collector.
- One aspect of the slurry for forming a protective film according to the present invention is: It contains the binder composition for electrical storage devices of any one example of the application example 1 thru
- the inorganic particles may be at least one particle selected from the group consisting of silica, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide.
- One aspect of the protective film according to the present invention is: It is produced using the protective film-forming slurry of Application Example 9 or Application Example 10.
- Application Example 12 One aspect of the electricity storage device according to the present invention is: The power storage device electrode according to Application Example 8 is provided.
- Application Example 13 One aspect of the electricity storage device according to the present invention is: The protective film of Application Example 11 is provided.
- a positive electrode and a negative electrode may be further provided, and the protective film may be in contact with at least one surface of the positive electrode and the negative electrode.
- a separator disposed between the positive electrode and the negative electrode can be further provided.
- a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode may be further provided, and a surface of the separator may be covered with the protective film.
- an electricity storage device electrode excellent in binding ability between active material particles, binding ability between active material particles and a current collector, and powder fall resistance, so-called adhesion is manufactured. can do.
- the electrical storage device provided with the electrical storage device electrode manufactured using the binder composition for electrical storage devices which concerns on this invention the discharge rate characteristic which is one of the electrical characteristics becomes very favorable.
- the electricity storage device including the protective film produced using the binder composition for an electricity storage device according to the present invention it is excellent in electrolyte permeability and liquid retention and can suppress an increase in internal resistance. That is, the power storage device according to the present invention has excellent charge / discharge characteristics because the degree of increase in the internal resistance of the power storage device is small even after repeated charge / discharge or overcharge.
- the said protective film is arrange
- FIG. 1 is an explanatory view schematically showing the concept of the major axis and the minor axis of the polymer particles (A).
- FIG. 2 is an explanatory view schematically showing the concept of the major axis and the minor axis of the polymer particles (A).
- FIG. 3 is an explanatory view schematically showing the concept of the major axis and the minor axis of the polymer particles (A).
- FIG. 4 is an explanatory view schematically showing the concept of irregularly shaped particles.
- FIG. 5 is an explanatory diagram schematically showing the concept of irregularly shaped particles.
- FIG. 6 is an explanatory view schematically showing the concept of irregularly shaped particles.
- FIG. 7 is an explanatory view schematically showing the concept of irregularly shaped particles.
- FIG. 1 is an explanatory view schematically showing the concept of the major axis and the minor axis of the polymer particles (A).
- FIG. 2 is an explanatory view schematically showing the concept of the major
- FIG. 8 is an explanatory view schematically showing the concept of irregularly shaped particles.
- FIG. 9 is an explanatory view schematically showing the concept of irregularly shaped particles.
- FIG. 10 is an explanatory view schematically showing the generation mechanism of irregularly shaped particles.
- FIG. 11 is an explanatory view schematically showing the generation mechanism of irregularly shaped particles.
- FIG. 12 is an explanatory view schematically showing the generation mechanism of irregularly shaped particles.
- FIG. 13 is a schematic diagram illustrating a cross section of the electricity storage device according to the first specific example.
- FIG. 14 is a schematic diagram illustrating a cross section of the electricity storage device according to the second specific example.
- FIG. 15 is a schematic diagram illustrating a cross section of an electricity storage device according to a third specific example.
- (meth) acrylic acid is a concept encompassing both “acrylic acid” and “methacrylic acid”.
- ⁇ (meth) acrylic acid ester is a concept encompassing both “ ⁇ acrylic acid ester” and “ ⁇ methacrylic acid ester”.
- Binder composition for an electricity storage device includes a repeating unit (a) derived from a fluorine-containing compound and a repeating unit (b) derived from a polyfunctional (meth) acrylate.
- DSC differential scanning calorimetry
- the polymer particle (A) and the liquid medium (B) are contained.
- One endothermic peak in the temperature range of 30 ° C. and one endothermic peak in the temperature range of 80 ° C. to 150 ° C. are observed.
- the binder composition for an electricity storage device according to the present embodiment is present in a latex state in which the polymer particles (A) are dispersed in the liquid medium (B).
- the binder composition for an electricity storage device is a binder for an electricity storage device electrode for improving the binding ability between active material particles, the adhesion adhesion between the active material particles and the current collector, and the powder fall resistance. It can be used as a composition (hereinafter referred to as “binder composition for electrodes” when used in this application), or a protective film for suppressing a short circuit caused by dendrid that occurs during charge and discharge. It can also be used as a binder composition for formation.
- binder composition for electrodes when used in this application
- binder composition for formation for formation.
- the polymer particles (A) contained in the binder composition for an electricity storage device according to this embodiment have a number average particle diameter (Da) in the range of 50 to 400 nm. It is preferable that the thickness is in the range of 100 to 250 nm.
- Da number average particle diameter
- the polymer particles can be sufficiently adsorbed on the surfaces of the active material particles and inorganic particles as described later. With the movement of the polymer particles, the polymer particles can also follow and move. As a result, since only one of the particles can be prevented from migrating alone, deterioration of electrical characteristics can be reduced.
- the number average particle diameter (Da) of the polymer particles (A) is a particle size distribution measured using a particle size distribution measuring apparatus based on the light scattering method, and the number of particles when particles are accumulated from small particles. This is the value of the particle diameter (D50) at which the cumulative frequency is 50%.
- a particle size distribution measuring apparatus include Coulter LS230, LS100, LS13 320 (above, manufactured by Beckman Coulter. Inc), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), and the like. These particle size distribution measuring devices are not intended to evaluate only primary particles of polymer particles, but can also evaluate secondary particles formed by aggregation of primary particles.
- the particle size distribution measured by these particle size distribution measuring devices can be used as an indicator of the dispersion state of the polymer particles (A) contained in the binder composition for an electricity storage device.
- the number average particle diameter (Da) of the polymer particles (A) is obtained by centrifuging a slurry for forming an electricity storage device electrode and a slurry for forming a protective film, which will be described later, to precipitate active material particles, It can also be measured by a method of measuring with a particle size distribution measuring apparatus.
- the polymer particles (A) contained in the binder composition for an electricity storage device according to the present embodiment have a ratio (Rmax / Rmin) of the major axis (Rmax) to the minor axis (Rmin) of 1.1 to 1.5. Preferably, it is in the range of 1.2 to 1.4.
- the ratio (Rmax / Rmin) is in the above range, the surface area of the polymer particles (A) increases and the surface of the polymer particles (A) is not a true spherical surface.
- the bonding ability between the inorganic particles, the adhesion ability between the current collector and the active material layer, and the adhesion ability between the protective film and the electrode or the separator are improved. As a result, the electrical characteristics of the electricity storage device are improved.
- the major axis (Rmax) of the polymer particle means the distance of the longest straight line among the straight lines connecting the end portions of the image of one independent polymer particle taken by a transmission electron microscope.
- the short diameter (Rmin) means the shortest diameter among straight lines connecting the end portions of the image.
- the major axis a of the elliptical shape is defined as the major axis (Rmax) of the polymer particle.
- the minor axis b is judged as the minor axis (Rmin) of the polymer particles.
- the major axis and minor axis (Rmin) of 10 polymer particles by measuring the major axis (Rmax) and minor axis (Rmin) of 10 polymer particles by the above-described determination method, and calculating the average value of the major axis (Rmax) and minor axis (Rmin), the major axis and The ratio to the minor axis (Rmax / Rmin) can be calculated and obtained.
- the polymer particles (A) are preferably “deformed particles” having a structure in which the first polymer particles and the second polymer particles are in close contact with each other.
- the polymer particle (A) can have a structure in which the other polymer particle is disposed on at least a part of the surface of one of the polymer particles.
- an irregular shape in the present specification means that two particles are arranged asymmetrically with respect to the center point of the whole particle.
- FIGS. 4 to 9 are explanatory views schematically showing the concept of irregularly shaped particles.
- Examples of the “irregular particles” include structures as shown in FIGS. 4 to 9.
- the second polymer particle 24a is in close contact with a part of the surface of the first polymer particle 22a, and the second polymer particle 24a is the first polymer particle 22a. It has a structure protruding from the surface.
- the deformed particle 20b shown in FIG. 5 includes the first polymer particle 22b completely including the second polymer particle 24b, and the second polymer particle 22b has a second weight at one point on the surface of the first polymer particle 22b. It is in contact with the coalesced particles 24b and has a substantially spherical structure as a whole.
- first polymer particle 22c and the second polymer particle 24c have a substantially spherical structure as a whole, with the first polymer particle 22c and the second polymer particle 24c being in close contact with each other.
- the first polymer particle 22c and the second polymer particle 24c have the same surface area, but this is not particularly limited.
- the deformed particle 20d shown in FIG. 7 includes the second polymer particle 24d inside the first polymer particle 22d, and the curved surface of the second polymer particle 24d appears on the surface of the deformed particle 20d. As a whole, it has a substantially spherical structure.
- the deformed particle 20e shown in FIG. 8 has a structure in which the deformed particle 20c shown in FIG. 6 is formed into an oval sphere like a rugby ball as a whole.
- the first polymer particle 22e and the second polymer particle 24e have the same surface area, but this point is not particularly limited.
- the deformed particle 20f shown in FIG. 9 has a substantially spherical first polymer particle 22f and a substantially spherical second polymer particle 24f in close contact with each other, and has a twin-spherical structure as a whole. Yes.
- the deformed particles that can be used in the present embodiment are preferably composed of the first polymer particles and the second polymer particles as described above.
- the composition of the first polymer particles and the composition of the second polymer particles may be the same or different, but at least of the monomer units contained in the first polymer particles.
- One type is preferably different from the monomer unit contained in the second polymer particle. That is, in this case, at least one kind of monomer units constituting the irregularly shaped particles is contained only in one of the first polymer particles and the second polymer particles. It will be. Accordingly, as shown in FIGS. 4 to 9, the first polymer particles and the second polymer particles can be asymmetrically separated.
- the major axis and minor axis of the irregularly shaped particles are measured as follows.
- the major axis (Rmax) is the second polymer particle from the end of the first polymer particle 22a. It is represented by the distance to the end of 24a.
- the short diameter (Rmin) is represented by the diameter of the larger particle (first polymer particle 22a in FIG. 4).
- the repeating unit which comprises polymer particle (A) The binder composition for electrical storage devices which concerns on this Embodiment is the repeating unit derived from the repeating unit (a) derived from a fluorine-containing compound, and polyfunctional (meth) acrylic acid ester The polymer particle (A) containing (b) is included.
- the repeating unit which comprises a polymer particle (A) is demonstrated.
- the polymer particles (A) contain a repeating unit (a) derived from a fluorine-containing compound.
- the repeating unit (a) derived from the fluorine-containing compound is preferably a repeating unit (a) derived from the fluorine-containing compound having an ethylenically unsaturated bond.
- Examples of the fluorine-containing compound having an ethylenically unsaturated bond include an olefin compound having a fluorine atom and a (meth) acrylic acid ester having a fluorine atom.
- Examples of the olefin compound having a fluorine atom include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, ethylene trifluoride chloride, and perfluoroalkyl vinyl ether.
- the (meth) acrylic acid ester having a fluorine atom for example, a compound represented by the following general formula (1), (meth) acrylic acid 3 [4 [1-trifluoromethyl-2,2-bis [bis (tri Fluoromethyl) fluoromethyl] ethynyloxy] benzooxy] 2-hydroxypropyl and the like.
- R 1 is a hydrogen atom or a methyl group
- R 2 is a C 1-18 hydrocarbon group containing a fluorine atom.
- R 2 in the general formula (1) examples include fluorinated alkyl groups having 1 to 12 carbon atoms, fluorinated aryl groups having 6 to 16 carbon atoms, and fluorinated aralkyl groups having 7 to 18 carbon atoms. It is preferably a fluorinated alkyl group having 1 to 12 carbon atoms.
- R 2 in the general formula (1) include, for example, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1, 3,3,3-hexafluoropropan-2-yl group, ⁇ - (perfluorooctyl) ethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,4,4,4- Hexafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 9H-perfluoro-1-nonyl group, 1H, 1H, 11H-perfluoroundecyl group, perfluorooctyl group, etc.
- the fluorine-containing compound having an ethylenically unsaturated bond is preferably an olefin compound having a fluorine atom, and is at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. It is particularly preferred. Only 1 type may be used for the said fluorine-containing compound which has an ethylenically unsaturated bond, and 2 or more types may be mixed and used for it. When the polymer particles (A) have the repeating unit (a), the oxidation resistance of the polymer particles tends to be good.
- the binder composition for an electricity storage device can be used for producing any of the positive electrode, the negative electrode, and the protective film, but from the viewpoint of imparting good oxidation resistance, It can be suitably used as a binder composition for forming a protective film or a binder composition for forming a protective film. This is because, when polymer particles having low oxidation resistance are used in the positive electrode or the protective film of the electricity storage device, good charge / discharge characteristics cannot be obtained because they are oxidized and decomposed by repeated charge / discharge.
- the content ratio of the repeating unit (a) in the polymer particles (A) is preferably 1 part by mass or more and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the polymer particles (A). preferable.
- the polymer particles (A) contain a repeating unit (b) derived from a polyfunctional (meth) acrylic acid ester.
- the repeating unit (b) When the polymer particles (A) contain the repeating unit (b), it becomes easy to produce irregular shaped particles as described above. That is, according to the example of the irregularly shaped particles shown in FIGS. 4 to 9 described above, the repeating unit (b) existing on the surface and / or the inside of the first polymer particle serving as the seed particle serves as a starting point or an opportunity. As a result, second polymer particles are formed. The generation mechanism will be described in detail later.
- polyfunctional means at least one selected from the group consisting of a polymerizable double bond, an epoxy group, and a hydroxyl group in addition to the polymerizable double bond of (meth) acrylic acid ester. It shows having a functional group.
- polyfunctional (meth) acrylic acid esters include glycidyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, allyl (meth) acrylate, and di (meth) acrylic acid.
- the content of the repeating unit (b) in the polymer particles (A) is preferably 1 to 10 parts by mass, and preferably 2 to 8 parts by mass with respect to 100 parts by mass of the polymer particles (A). More preferred. It is preferable for the content ratio to be in the above-mentioned range since it becomes easy to produce irregular shaped particles as described above. When the content ratio is less than the above range, the ground contact area between the particles becomes small, so the first polymer particles and the second polymer particles may not be in close contact, and irregularly shaped particles may not be produced. On the other hand, when the content ratio exceeds the above range, the entire surface of the seed particle is covered with the repeating unit (b), so that it may become a so-called core-shell particle and the irregularly shaped particle may not be produced.
- the polymer particles (A) preferably have a quantitative ratio of the repeating unit (a) to the repeating unit (b) in the range of 2: 1 to 10: 1 on a mass basis. More preferably, it is in the range of 9: 1.
- a quantitative ratio in the above range is preferable because it becomes easier to produce irregularly shaped particles as described above.
- the polymer particles (A) preferably further contain a repeating unit (c) derived from an unsaturated carboxylic acid.
- a repeating unit (c) derived from an unsaturated carboxylic acid a slurry for an electricity storage device electrode and a slurry for forming a protective film using the binder composition for an electricity storage device according to the present embodiment (Hereinafter, these are collectively referred to simply as “slurry”), and the stability is improved.
- unsaturated carboxylic acid examples include mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and one or more selected from these. Can be. In particular, at least one selected from acrylic acid, methacrylic acid and itaconic acid is preferable.
- the content of the repeating unit (c) in the polymer particles (A) is preferably 15 parts by mass or less, and 0.3 to 10 parts by mass with respect to 100 parts by mass of the polymer particles (A). Is more preferably 1 to 10 parts by mass.
- the content ratio of the repeating unit (c) is in the above range, the dispersion stability of the polymer particles (A) is excellent during the slurry preparation, and aggregates are hardly generated. Further, an increase in slurry viscosity over time can be suppressed.
- the polymer particle (A) preferably further contains a repeating unit (d) derived from a monofunctional (meth) acrylic ester.
- the obtained polymer particle (A) has an appropriate affinity for the electrolytic solution.
- “monofunctional” is selected from the group consisting of a polymerizable double bond, an epoxy group, a hydroxyl group and a carboxylic acid in addition to the polymerizable double bond of (meth) acrylic acid ester. It indicates that it does not have at least one functional group.
- monofunctional (meth) acrylate esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, N-butyl (meth) acrylate, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, Examples include 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, and the like, and one or more selected from these.
- methyl (meth) acrylate one or more selected from methyl (meth) acrylate, ethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is preferable, and methyl (meth) acrylate is particularly preferable. preferable.
- the content ratio of the repeating unit (d) in the polymer particles (A) is preferably 40 parts by mass or more and more preferably 45 parts by mass or more with respect to 100 parts by mass of the polymer particles (A). .
- the resulting polymer particles (A) have an appropriate affinity with the electrolytic solution, and the internal content of the binder as an electrical resistance component in the electricity storage device. While suppressing a raise of resistance, the fall of adhesiveness by absorbing electrolyte excessively can be prevented.
- the polymer particles (A) preferably further contain a repeating unit (e) derived from an ⁇ , ⁇ -unsaturated nitrile compound.
- a repeating unit (e) derived from an ⁇ , ⁇ -unsaturated nitrile compound.
- the swelling property with respect to the electrolyte solution of polymer particle (A) can be improved more. That is, the presence of a nitrile group makes it easier for the solvent to enter the network structure composed of polymer chains and the network interval is widened, so that the solvated lithium ions can easily move through the network structure. Thereby, it is thought that the diffusibility of lithium ion improves, As a result, electrode resistance falls and it can implement
- ⁇ , ⁇ -unsaturated nitrile compound examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, vinylidene cyanide, and the like. Can be. Among these, at least one selected from acrylonitrile and methacrylonitrile is preferable, and acrylonitrile is particularly preferable.
- the content ratio of the repeating unit (e) in the polymer particles (A) is preferably 35 parts by mass or less, more preferably 10 to 25 parts by mass with respect to 100 parts by mass of the polymer particles (A). preferable.
- the content ratio of the repeating unit (e) is in the above range, the compatibility with the electrolyte solution to be used is excellent, and the swelling rate does not become too large, which can contribute to the improvement of battery characteristics.
- the polymer particles (A) may further contain a repeating unit (f) derived from a conjugated diene compound.
- a conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like. It can be one or more selected from these.
- the content rate of the repeating unit (f) in a polymer particle (A) can be 35 mass parts or less with respect to 100 mass parts of polymer particles (A).
- the polymer particles (A) may further contain a repeating unit (g) derived from an aromatic vinyl compound.
- the aromatic vinyl compound include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene and the like.
- the content rate of the repeating unit (g) in a polymer particle (A) can be 50 mass parts or less with respect to 100 mass parts of polymer particles (A).
- the polymer particles (A) may further contain repeating units derived from compounds other than those described above, if necessary.
- specific examples of other compounds include alkyl amides of ethylenically unsaturated carboxylic acids such as (meth) acrylamide and N-methylol acrylamide; vinyl carboxylic acid esters such as vinyl acetate and vinyl propionate; ethylenically unsaturated dicarboxylic acids An amino acid amide of ethylenically unsaturated carboxylic acid such as aminoethyl acrylamide, dimethylaminomethyl methacrylamide, methylaminopropyl methacrylamide, etc., and one or more selected from these be able to.
- the particles when used as a binder composition for an electrode, the particles are better than the active material layer. Flexibility and tackiness can be imparted, and therefore adhesion can be further improved.
- the particles when used as a binder composition for forming a protective film, the particles can impart good flexibility and tackiness to the protective film, and therefore the adhesion can be further improved.
- the other temperature of the endothermic peak of the polymer particles (A) is less than the above range, the polymer may be deteriorated, so that stable charge / discharge characteristics cannot be achieved.
- 80 ⁇ It is common to dry by heating to about 150 ° C.
- the wettability of the contact surface between the active material or inorganic particle surface and the polymer particles changes, and the polymer particles can be bonded more firmly. Therefore, when the other endothermic peak temperature of the polymer particles (A) is in the range of 80 ° C. to 150 ° C., the binding ability between the active material or inorganic particles and the polymer particles can be improved, and the electricity storage device Deterioration of the polymer during use can be effectively prevented.
- THF Tetrahydrofuran
- the THF insoluble content of the polymer particles (A) is preferably 80% or more, and more preferably 90% or more.
- the THF-insoluble content is estimated to be approximately proportional to the amount of insoluble content in the electrolytic solution used in the electricity storage device. For this reason, if THF insoluble content is the said range, even when an electrical storage device is produced and charging / discharging is repeated over a long period of time, elution of the polymer particle (A) to electrolyte solution can be suppressed.
- the polymer particles (A) contained in the binder composition for an electricity storage device according to the present embodiment have a particularly limited synthesis method as long as the polymer particles (A) have the above-described configuration. However, it can be easily synthesized by, for example, a known emulsion polymerization process or a suitable combination thereof. For example, it can be produced by the method described in JP-A-2007-197588.
- the polymer particles (A) contained in the binder composition for an electricity storage device according to the present embodiment can be specifically produced according to the method shown below.
- the first polymer particles can be obtained by a usual emulsion polymerization method using an aqueous medium.
- the “aqueous medium” means a medium containing water as a main component. Specifically, the water content in the aqueous medium is preferably 40% by mass or more, and more preferably 50% by mass or more.
- Other media that can be used in combination with water include compounds such as esters, ketones, phenols, and alcohols.
- the conditions for emulsion polymerization may be in accordance with known methods. For example, when the total amount of monomers used is 100 parts, usually 100 to 500 parts of water is used, and the polymerization temperature is -10 to 100 ° C. (preferably -5 to 100 ° C., more preferably 0 to 90 ° C.). ) And a polymerization time of 0.1 to 30 hours (preferably 2 to 25 hours).
- a method of emulsion polymerization a batch method in which monomers are charged all together, a method in which monomers are divided or continuously supplied, a method in which a monomer pre-emulsion is divided or continuously added, or these A method that combines methods in stages can be adopted.
- the molecular weight regulator used for normal emulsion polymerization, a chelating agent, an inorganic electrolyte, etc. can be used 1 type, or 2 or more types as needed.
- persulfates such as potassium persulfate and ammonium persulfate; diisopropyl peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, tert-butylperoxy-2 Organic peroxides such as ethylhexanoate; azo compounds such as azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2-carbamoylazaisobutyronitrile; having a peroxide group
- a reducing agent such as a radical emulsifier containing a radical emulsifying compound, sodium hydrogen sulfite, and ferrous sulfate is combined can be used.
- molecular weight regulator used for emulsion polymerization.
- molecular weight regulators include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, thioglycolic acid Mercaptans such as dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, etc .; Xanthogen disulfides such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide; chloro
- Terunepin can include dipentene, 1,1-diphenylethylene and the like. These molecular weight regulators can be used singly or in combination of two or more. Of these, mercaptans, xanthogen disulfides, thiuram disulfides, 1,1-diphenylethylene, ⁇ -methylstyrene dimer and the like are more preferably used.
- emulsifier used in the emulsion polymerization examples include an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorosurfactant.
- anionic surfactant examples include sulfates of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, sulfates of polyethylene glycol alkyl ethers, etc .; examples of the nonionic surfactants include polyethylene glycol Examples thereof include alkyl esters, alkyl ethers of polyethylene glycol, alkyl phenyl ethers of polyethylene glycol, and the like.
- the anion portion is composed of carboxylate, sulfate ester salt, sulfonate salt or phosphate ester salt
- the cation portion is composed of amine salt, quaternary ammonium salt or the like. Things can be mentioned.
- amphoteric surfactants include betaine compounds such as lauryl betaine and stearyl betaine; amino acid type surfactants such as lauryl- ⁇ -alanine, lauryl di (aminoethyl) glycine, and octyldi (aminoethyl) glycine.
- An agent can be mentioned.
- fluorosurfactant examples include fluorobutyl sulfonate, phosphoric acid ester having a fluoroalkyl group, carboxylate having a fluoroalkyl group, and a fluoroalkyl ethylene oxide adduct.
- fluorosurfactants examples include F-top EF301, EF303, and EF352 (above, manufactured by Tochem Products Co., Ltd.); Megafac F171, F172, F173 (above, manufactured by DIC Corporation); FC430, FC431 (above, manufactured by Sumitomo 3M Limited); Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30, KH-40 (above, manufactured by Asahi Glass Co., Ltd.); tergent 250, 251, 222F, FTX-218 (above, manufactured by Neos Co., Ltd.), and the like.
- an emulsifier the 1 type (s) or 2 or more types selected from the above can be used.
- the polymerization conversion rate of the monomer at the end of the emulsion polymerization is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- the obtained first polymer particles are usually substantially spherical particles.
- the monomer for the second polymer particles is polymerized. More specifically, the second polymer particles are formed by seed-polymerizing the monomer for the second polymer particles in a state where the obtained first polymer particles are used as seed particles.
- the second polymer particle monomer or a pre-emulsion thereof may be added all at once, in a divided manner, or continuously in an aqueous medium in which the first polymer particles are dispersed.
- the amount of the first polymer particles used at this time is preferably 1 to 100 parts by mass, and preferably 2 to 80 parts by mass with respect to 100 parts by mass of the monomer for the second polymer particles. It is more preferable.
- an initiator or an emulsifier is used in the polymerization, the same one as used in the production of the first polymer particles can be used.
- the conditions such as the polymerization time may be the same as in the production of the first polymer particles.
- 10 to 12 are explanatory views schematically showing the generation mechanism of irregularly shaped particles.
- the second polymer particle monomer 23 when the second polymer particle monomer 23 is introduced into the aqueous medium in which the first polymer particles 22 are dispersed, the second polymer particle monomer is introduced. Most of 23 is normally occluded once by the first polymer particles, and the polymerization is started in or on the surface of the first polymer particles 22.
- the second polymer particle monomer 23 decreases in compatibility with the first polymer particle 22 as the polymerization proceeds, and phase-separates with the first polymer particle 22. Therefore, at the initial stage of the polymerization, the polymerization can proceed at a plurality of locations of the first polymer particles 22 as shown in FIG.
- the second polymer particles 24 tend to form a single second polymer particle 24 in which the polymers polymerized at various locations of the first polymer particle 22 gather together. Then, when the second polymer particle 24 grows to a certain size, the subsequent polymerization proceeds mainly by the second polymer particle 24 as shown in FIG. In this way, deformed particles in which the first polymer particles and the second polymer particles are asymmetrically separated are formed.
- the mass ratio (first / second) between the first polymer particles and the second polymer particles is 2/98 to 98/2. It is preferably 5/95 to 95/5.
- the ratio of the exposed surface formed by the first polymer particles to the exposed surface formed by the second polymer particles in the total surface area of the irregularly shaped particles is It is preferably 5/95 to 95/5, and more preferably 10/90 to 90/10.
- the proportion of either one of the first polymer particles and the second polymer particles is less than the above range, the effect due to the irregular particles being “abnormal” may not be sufficiently obtained.
- the ratio of the exposed surface of each primary particle which occupies for the total surface area of a deformed particle can be measured from an electron micrograph, for example.
- the shape of the irregularly shaped particles is the mass ratio between the first polymer particles and the second polymer particles, the separability between the first polymer particles and the second polymer particles, and the second polymer particles.
- Various changes occur depending on the polymerization conditions and the like when forming. For example, when the mass ratio between the first polymer particles and the second polymer particles and the polymerization conditions are constant, as the separability between the first polymer particles and the second polymer particles increases, The shape of irregularly shaped particles tends to change in the order of FIG. 5, FIG. 7, and FIG.
- the binder composition for an electricity storage device contains a liquid medium (B).
- the liquid medium (B) is preferably an aqueous medium containing water.
- This aqueous medium can contain a small amount of non-aqueous medium in addition to water. Examples of such non-aqueous media include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, sulfone compounds, and the like, and one or more selected from these are used. can do.
- the content ratio of such a non-aqueous medium is preferably 10 parts by mass or less, more preferably 5 parts by mass or less with respect to 100 parts by mass of the aqueous medium, and only water without containing the non-aqueous medium. It is most preferable that it consists of.
- the binder composition for an electricity storage device uses an aqueous medium as a medium, and preferably contains no non-aqueous medium other than water, so that it has a low adverse effect on the environment and is safe for handling workers. Increases the nature.
- the binder composition for an electricity storage device according to the present embodiment may further contain other additives as necessary in addition to the polymer particles (A) and the liquid medium (B) described above. it can.
- a thickener can be contained from the viewpoint of further improving the applicability and the charge / discharge characteristics of the electricity storage device.
- thickeners examples include cellulose compounds such as carboxymethylcellulose, methylcellulose, and hydroxypropylcellulose; ammonium salts or alkali metal salts of the above cellulose compounds; poly (meth) acrylic acid, modified poly (meth) acrylic acid, and the like.
- a water-soluble polymer such as a saponified product of a copolymer of an unsaturated carboxylic acid and a vinyl ester.
- particularly preferred thickeners are alkali metal salts of carboxymethyl cellulose, alkali metal salts of poly (meth) acrylic acid, and the like.
- Examples of commercially available products of these thickeners include CMC1120, CMC1150, CMC2200, CMC2280, and CMC2450 (manufactured by Daicel Corporation) as alkali metal salts of carboxymethylcellulose.
- the use ratio of the thickener is preferably 15% by mass with respect to the total solid content in the binder composition for an electricity storage device. Or less, more preferably 0.1 to 10% by mass.
- Power storage device electrode slurry The power storage device electrode slurry according to the present embodiment can be produced using the power storage device binder composition described above.
- the slurry for an electricity storage device electrode refers to a dispersion used to form an active material layer on the surface of the current collector after being applied to the surface of the current collector and then dried.
- the slurry for an electricity storage device electrode according to the present embodiment contains the aforementioned binder composition for an electricity storage device, an active material, and water.
- each component contained in the slurry for an electricity storage device electrode according to the present embodiment will be described in detail. However, the components contained in the binder composition for an electricity storage device are omitted because they are as described above.
- Active material there is no restriction
- the positive electrode active material is not particularly limited as long as it is a positive electrode material that can be doped / undoped with lithium and contains a sufficient amount of lithium.
- An atom-containing oxide is preferable, and a lithium atom-containing oxide having an olivine structure is more preferable.
- the lithium atom-containing oxide having the olivine structure is a compound represented by the following general formula (2) and having an olivine type crystal structure.
- Li 1-x M x (XO 4 ) (2) (Wherein M is at least a metal ion selected from the group consisting of Mg, Ti, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, Ge, and Sn)
- X is at least one selected from the group consisting of Si, S, P and V;
- x is a number, and depending on the valence of M and (XO 4 ), the formula (2 )
- the overall valence is selected to be zero, and satisfies the relationship 0 ⁇ x ⁇ 1.)
- the lithium atom-containing oxide having the olivine structure has different electrode potentials depending on the type of the metal element M. Therefore, the battery voltage can be arbitrarily set by selecting the type of the metal element M.
- Typical examples of the lithium atom-containing oxide having an olivine structure include LiFePO 4 , LiCoPO 4 , Li 0.90 Ti 0.05 Nb 0.05 Fe 0.30 Co 0.30 Mn 0.30 PO 4, and the like. Can be mentioned. Among these, LiFePO 4 is particularly preferable because it is easy to obtain an iron compound as a raw material and is inexpensive.
- the negative electrode active material for example, a carbon material, a crystalline or amorphous metal oxide, or the like can be suitably used.
- carbon materials include non-graphitizable carbon materials such as coke and glassy carbon, and graphites of highly crystalline carbon materials having a developed crystal structure. Specifically, pyrolytic carbons, cokes ( Pitch coke, needle coke, petroleum coke, etc.), graphite, glassy carbons, polymer compound fired bodies (phenol resins, furan resins, etc. fired and carbonized at an appropriate temperature), carbon fibers, activated carbon, etc. Can be mentioned.
- Examples of crystalline or amorphous metal oxides include magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn ), Lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) or platinum (Pt) ) As a constituent element.
- the number average particle diameter (Db) of the active material is preferably in the range of 0.4 to 10 ⁇ m, and more preferably in the range of 0.5 to 7 ⁇ m when the active material is a positive electrode active material.
- the number average particle diameter (Db) of the positive electrode active material is within the above range, the diffusion distance of lithium in the positive electrode active material is shortened, so that the resistance associated with lithium desorption / insertion during charge / discharge can be reduced. As a result, the charge / discharge characteristics are further improved.
- the contact area between the cathode active material and the conductivity-imparting agent is sufficient because the average particle diameter (Db) of the cathode active material is within the above range. Therefore, the electronic conductivity of the electrode is improved, and the electrode resistance is further reduced.
- the number average particle size (Db) of the active material is preferably in the range of 1 to 50 ⁇ m, more preferably in the range of 5 to 40 ⁇ m, and 10 to 30 ⁇ m. It is especially preferable that it is in the range.
- the number average particle diameter (Db) of the negative electrode active material is in the above range, the aggregation of the negative electrode active material particles in the negative electrode slurry can be suppressed, and the negative electrode active material layer has a uniform distribution of the negative electrode active material particles. Since the fabrication becomes easy, the power storage characteristics of the power storage device can be improved.
- the number average particle diameter (Db) of the active material is the accumulation of the number of particles when the particle size distribution is measured using a particle size distribution measuring apparatus based on a laser diffraction method and the particles are accumulated from small particles. This is the value of the particle diameter (D50) at which the frequency is 50%.
- a laser diffraction type particle size distribution measuring apparatus examples include HORIBA LA-300 series, HORIBA LA-920 series (above, manufactured by Horiba, Ltd.) and the like. This particle size distribution measuring apparatus does not only evaluate primary particles of the active material, but also evaluates secondary particles formed by aggregation of the primary particles.
- the number average particle diameter (Db) obtained by the particle size distribution measuring apparatus can be used as an index of the dispersion state of the active material contained in the slurry for the electricity storage device electrode.
- the number average particle diameter (Db) of the active material is measured by centrifuging the slurry for power storage device electrodes to precipitate the active material, then removing the supernatant, and measuring the precipitated active material by the above method. Can also be measured.
- the said slurry for electrical storage device electrodes can contain components other than the component mentioned above as needed. Examples of such components include a conductivity-imparting agent, a non-aqueous medium, and a thickener.
- conductivity-imparting agent examples include carbon in a lithium ion secondary battery; in a nickel-hydrogen secondary battery, cobalt oxide at the positive electrode: nickel powder, cobalt oxide, titanium oxide, carbon at the negative electrode Etc. are used respectively.
- examples of carbon include graphite, activated carbon, acetylene black, furnace black, graphite, carbon fiber, and fullerene. Among these, acetylene black or furnace black can be preferably used.
- the use ratio of the conductivity-imparting agent is preferably 20 parts by mass or less, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the active material.
- the slurry for an electricity storage device electrode may contain a non-aqueous medium having a normal boiling point of 80 to 350 ° C. from the viewpoint of improving the applicability.
- a non-aqueous medium include amide compounds such as N-methylpyrrolidone, dimethylformamide, N, N-dimethylacetamide; hydrocarbons such as toluene, xylene, n-dodecane, tetralin; 2-ethyl- Alcohols such as 1-hexanol, 1-nonanol and lauryl alcohol; ketones such as methyl ethyl ketone, cyclohexanone, phorone, acetophenone and isophorone; esters such as benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate and butyl lactate; o-toluidine, m
- examples include amine compounds such as toluidine
- the said slurry for electrical storage device electrodes can contain a thickener from a viewpoint of improving the coating property.
- Specific examples of the thickener include various compounds described in the above-mentioned “1.3. Other additives”.
- the use ratio of the thickener is preferably 20% by mass or less, more preferably 0. 0% by weight based on the total solid content of the slurry for power storage device electrodes. It is 1 to 15% by mass, and particularly preferably 0.5 to 10% by mass.
- the slurry for power storage device electrode according to the present embodiment is a mixture of the binder composition for power storage device, the active material, water, and an additive used as necessary. Can be manufactured. These can be mixed by stirring by a known method. For example, a stirrer, a defoamer, a bead mill, a high-pressure homogenizer, or the like can be used.
- the preparation of the slurry for an electricity storage device electrode is preferably performed at least part of the process under reduced pressure. Thereby, it can prevent that a bubble arises in the electrode layer obtained.
- the degree of pressure reduction is preferably about 5.0 ⁇ 10 3 to 5.0 ⁇ 10 5 Pa as an absolute pressure.
- the mixing and stirring for producing the slurry for the electricity storage device electrode it is necessary to select a mixer that can stir to such an extent that no agglomerates of the active material remain in the slurry and sufficient dispersion conditions as necessary.
- the degree of dispersion can be measured by a particle gauge, but it is preferable to mix and disperse so that aggregates larger than at least 100 ⁇ m are eliminated.
- the mixer that meets such conditions include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a Hobart mixer, and the like.
- the ratio (Da / Db) of the number average particle diameter (Da) of the polymer particles (A) and the number average particle diameter (Db) of the active material contained in the binder composition for an electricity storage device described above is , Preferably in the range of 0.01 to 1.0, more preferably in the range of 0.05 to 0.5.
- the technical meaning of this is as follows.
- At least one of the polymer particles and the active material migrates in the step of drying the formed coating film after applying the slurry for the electricity storage device electrode to the surface of the current collector. That is, the particles move along the thickness direction of the coating film by receiving the action of surface tension. More specifically, at least one of the polymer particles and the active material moves to the side of the coating film surface opposite to the surface in contact with the current collector, that is, the gas-solid interface side where water evaporates. . When such migration occurs, the distribution of the polymer particles and the active material becomes non-uniform in the thickness direction of the coating film, causing problems such as deterioration of electrode characteristics and loss of adhesion.
- the ratio of the number average particle diameter of both particles (Da / Db) is in the above range, it is possible to suppress the occurrence of the problems as described above, and to achieve both the electrical characteristics and the good adhesion.
- the device electrode can be easily manufactured.
- the ratio (Da / Db) is less than the above range, the difference between the average particle diameters of the polymer particles and the active material is small, so the area where the polymer particles and the active material are in contact with each other is small, and the powder fall resistance is not good. May be sufficient.
- the slurry for the electricity storage device electrode according to the present embodiment preferably has a solid content concentration (a ratio of the total mass of components other than the solvent in the slurry to the total mass of the slurry) of 20 to 80% by mass. 30 to 75% by mass is more preferable.
- the slurry for the electricity storage device electrode according to the present embodiment preferably has a spinnability of 30 to 80%, more preferably 33 to 79%, and particularly preferably 35 to 78%.
- spinnability is less than the above range, the leveling property may be insufficient when the slurry for an electricity storage device electrode is applied onto the current collector, and thus the electrode thickness may not be uniform.
- an electricity storage device electrode having a non-uniform thickness is used, an in-plane distribution of charge / discharge reaction occurs, making it difficult to develop stable battery performance.
- the spinnability exceeds the above range, dripping is likely to occur when the slurry for the electricity storage device electrode is applied on the current collector, and the electricity storage device electrode having a stable quality may not be obtained. Therefore, if the spinnability is in the above range, the occurrence of these problems can be suppressed, and it becomes easy to produce an electricity storage device electrode that achieves both good electrical characteristics and adhesion. .
- the “threadability” in the present specification is measured as follows. First, a Zaan cup (made by Dazai Equipment Co., Ltd., Zaan Bisco City Cup No. 5) having an opening with a diameter of 5.2 mm at the bottom is prepared. With this opening being closed, 40 g of slurry for an electricity storage device electrode is poured into the Zahn cup. Then, when an opening part is open
- T 0 when opening the opening the T A when the thread has finished slurry for an electricity storage device electrode, when the when the outflow of the slurry for an electricity storage device electrodes is terminated and the T B, hereby
- the electricity storage device electrode according to the present embodiment includes a current collector and a layer formed by applying and drying the above-mentioned slurry for an electricity storage device electrode on the surface of the current collector. is there.
- Such an electricity storage device electrode can be manufactured by applying the aforementioned slurry for an electricity storage device electrode to the surface of an appropriate current collector such as a metal foil to form a coating film, and then drying the coating film. .
- the power storage device electrode thus manufactured has an active material layer containing the above-described polymer particles (A) and an active material, and optionally added optional components, on a current collector. It will be.
- Such an electricity storage device electrode has excellent adhesion between the current collector and the active material layer, and also has good charge / discharge rate characteristics, which is one of electrical characteristics.
- the current collector is not particularly limited as long as it is made of a conductive material.
- a current collector made of metal such as iron, copper, aluminum, nickel, and stainless steel is used.
- aluminum is used for the positive electrode and copper is used for the negative electrode, the above-mentioned storage device is used.
- the effect of the slurry for an electricity storage device electrode manufactured using a binder is most apparent.
- a punching metal, an expanded metal, a wire mesh, a foam metal, a mesh metal fiber sintered body, a metal plated resin plate, or the like is used.
- the shape and thickness of the current collector are not particularly limited, but it is preferable that the current collector be a sheet having a thickness of about 0.001 to 0.5 mm.
- the coating can be performed by an appropriate method such as a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a dipping method, or a brush coating method.
- the coating amount of the power storage device electrode slurry is not particularly limited, but the active material layer formed after the liquid medium is removed preferably has an amount of 0.005 to 5 mm, preferably 0.01 to 2 mm. It is more preferable to set the amount to be.
- drying method from the coated film after coating (method for removing water and optionally used non-aqueous medium); for example, drying with warm air, hot air, low humidity air; vacuum drying; (far) infrared , Drying by irradiation with an electron beam or the like.
- the drying speed is appropriately set so that the liquid medium can be removed as quickly as possible within a speed range in which the active material layer does not crack due to stress concentration or the active material layer does not peel from the current collector. be able to.
- the density of the active material layer by pressing the dried active material layer.
- the pressing method include a mold press and a roll press.
- the density of the active material layer after pressing is preferably 1.6 to 2.4 g / cm 3, and more preferably 1.7 to 2.2 g / cm 3 .
- the protective film-forming slurry according to the present embodiment contains the above-described binder composition for an electricity storage device (a binder composition for forming a protective film) and inorganic particles.
- the slurry for forming a protective film is a dispersion used for forming a protective film on the surface of the electrode or the separator or both by applying the slurry to the surface or both of the electrode and the separator and then drying the slurry.
- Fluorine-containing organic polymers, polyamides, polyimides, and polyamideimides in the prior art have been used extensively in electricity storage devices because of their excellent oxidation resistance, but they do not satisfy the severe demands for the rate of increase in resistance in recent years. There wasn't.
- the present inventors have formed a protective film containing polymer particles (A) containing a specific repeating unit as described above and having an endothermic peak observed in a specific range.
- the present inventors have found that the protective film produced from the slurry for use does not increase the internal resistance of the electricity storage device and can reduce the rate of increase in resistance.
- the polymer particles (A) contained in the protective film-forming binder composition are used in an amount of 5 to 50 parts by mass of the repeating unit (a) derived from the fluorine-containing compound with respect to 100 parts by mass of the polymer particles (A). And 1 to 10 parts by mass of the repeating unit (c) derived from the unsaturated carboxylic acid. Since such polymer particles (A) can firmly capture inorganic particles, both lithium ion permeability and improved toughness in the formed protective film can be achieved. As a result, the resistance increase rate can be further reduced.
- the protective film-forming slurry according to the present embodiment can improve the toughness of the formed protective film by containing inorganic particles.
- the inorganic particles at least one particle selected from the group consisting of silica, titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), and magnesium oxide (magnesia) can be used.
- titanium oxide and aluminum oxide are preferable from the viewpoint of further improving the toughness of the protective film.
- rutile type titanium oxide is more preferable.
- the number average particle diameter (Db) of the inorganic particles is preferably 1 ⁇ m or less, and more preferably in the range of 0.1 to 0.8 ⁇ m.
- the number average particle diameter (Db) of the inorganic particles is within the above range, a smooth and flexible protective film can be formed, and when an electricity storage device is produced, it comes into contact with a separator or electrode disposed adjacent to the protective film. However, since the risk of damaging them is reduced, the durability of the electricity storage device is improved.
- the number average particle diameter (Db) of an inorganic particle is larger than the average hole diameter of the separator which is a porous film. Thereby, the damage to a separator can be reduced and it can prevent that an inorganic particle is clogged with the microporous of a separator.
- the number average particle diameter (Db) of the inorganic particles is the accumulation of the number of particles when the particle size distribution is measured using a particle size distribution measuring apparatus based on the laser diffraction method and the particles are accumulated from small particles. This is the value of the particle diameter (D50) at which the frequency is 50%.
- a laser diffraction particle size distribution measuring apparatus examples include HORIBA LA-300 series, HORIBA LA-920 series (above, manufactured by Horiba, Ltd.), and the like. This particle size distribution measuring apparatus is not intended to evaluate only primary particles of inorganic particles, but also targets secondary particles formed by aggregation of primary particles.
- the number average particle diameter (Db) obtained by this particle size distribution measuring apparatus can be used as an indicator of the dispersion state of the inorganic particles contained in the protective film-forming slurry.
- the average particle diameter (Db) of the inorganic particles is measured by centrifuging the protective film-forming slurry and allowing the inorganic particles to settle, then removing the supernatant and measuring the precipitated inorganic particles by the above method. Can also be measured.
- the protective film-forming slurry according to the present embodiment can contain other components such as a conductivity-imparting agent, water, a non-aqueous medium, a thickener, and a surfactant as necessary.
- the protective film-forming slurry according to the present embodiment can contain water. By containing water, the stability of the slurry for forming the protective film is improved, and the protective film can be produced with good reproducibility. Water has a higher evaporation rate than commonly used high-boiling solvents (for example, N-methylpyrrolidone, etc.), and is effective in improving productivity and reducing particle migration by shortening the solvent removal time. Can be expected.
- commonly used high-boiling solvents for example, N-methylpyrrolidone, etc.
- the water in the protective film-forming slurry is only from the water brought in from the binder composition for an electricity storage device. Or may be the total of water brought in from the binder composition for an electricity storage device and newly added water.
- Non-aqueous medium As the non-aqueous medium, the materials and addition amounts described in the above "2.2.2 Non-aqueous medium” can be used as necessary. Among these, when the binder composition for an electricity storage device contains water as a liquid medium, it is preferable to mix with water.
- the thickener various compounds described in the above-mentioned "1.3. Other additives" can be mentioned.
- the use ratio of the thickener is preferably 20% by mass or less, more preferably 0. 0% by mass with respect to the total solid content of the slurry for the electricity storage device electrode. It is 1 to 15% by mass, and particularly preferably 0.5 to 10% by mass.
- the slurry for forming a protective film according to the present embodiment can contain a surfactant from the viewpoint of improving its dispersibility and dispersion stability.
- examples of the surfactant include those described in “1.1.4. Production method of polymer particles (A)”.
- the binder composition for an electricity storage device described above is 0.1 to 20 mass in terms of solid content with respect to 100 parts by mass of inorganic particles. It is preferably contained in an amount of 1 to 10 parts by mass.
- the content ratio of the binder composition for an electricity storage device is 0.1 to 10 parts by mass in terms of solid content, the balance between the toughness of the protective film to be formed and the lithium ion permeability is improved. The rate of increase in resistance of the obtained electricity storage device can be further reduced.
- the slurry for forming a protective film according to this embodiment is prepared by mixing the binder composition for an electricity storage device as described above, the inorganic particles as described above, and other components used as necessary. Is done.
- a known mixing device such as a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a Hobart mixer can be used.
- a mixer capable of stirring to such an extent that the aggregate of inorganic particles does not remain in the slurry and a sufficient dispersion condition as necessary are selected.
- the degree of dispersion is preferably mixed and dispersed so that aggregates larger than at least 20 ⁇ m are eliminated.
- the degree of dispersion can be measured with a grain gauge.
- the slurry for forming a protective film for an electricity storage device as described above has excellent adhesion between inorganic particles, between inorganic particles and electrodes, and between inorganic particles and separators by containing the above-mentioned binder composition for electricity storage devices.
- An electricity storage device electrode provided with a protective film can be formed, and an electricity storage device provided with such an electricity storage device electrode has a sufficiently low resistance increase rate.
- the protective film according to the present embodiment can be formed by applying and drying the above-described protective film-forming slurry on the surface of the positive electrode, the negative electrode, or the separator.
- the coating can be performed by an appropriate method such as a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a dipping method, or a brush coating method.
- the coating amount of the protective film-forming slurry is not particularly limited, but it is preferable that the thickness of the protective film formed after removing the liquid medium is 0.5 to 4 ⁇ m, preferably 0.5 to 3 ⁇ m. It is more preferable to set it as an amount. When the thickness of the protective film is in the above range, the permeability of the electrolytic solution into the electrode and the liquid retaining property are improved, and an increase in the internal resistance of the electrode can be suppressed.
- drying method from the coated film after coating (method for removing water and optionally used non-aqueous medium); for example, drying with warm air, hot air, low humidity air; vacuum drying; (far) infrared , Drying by irradiation with an electron beam or the like.
- the drying speed can be appropriately set so that the liquid medium can be removed as quickly as possible within a speed range in which the protective film does not crack due to stress concentration.
- the coating film is preferably dried at a temperature of 20 to 250 ° C., more preferably 50 to 150 ° C., preferably for 1 to 120 minutes, more preferably 5 to 60 minutes. be able to.
- Electric storage device 6.1. 1st Embodiment The electrical storage device which concerns on one Embodiment of this invention is equipped with the electrical storage device electrode mentioned above, Furthermore, electrolyte solution is contained and it can manufacture according to a conventional method using components, such as a separator. As a specific manufacturing method, for example, a negative electrode and a positive electrode are overlapped via a separator, and this is wound into a battery container according to a battery shape, put into a battery container, an electrolyte is injected into the battery container, and sealing is performed. The method of doing is mentioned.
- the shape of the battery can be an appropriate shape such as a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, or a flat shape.
- the electrolytic solution may be liquid or gel, and a material that effectively expresses the function as a battery may be selected from known electrolytic solutions used for the electricity storage device, depending on the type of active material.
- the electrolytic solution can be a solution in which an electrolyte is dissolved in a suitable solvent.
- any conventionally known lithium salt can be used, and specific examples thereof include, for example, LiClO 4 , LiBF 4 , LiPF 6 , LiCF 3 CO 2 , LiAsF. 6 , LiSbF 6 , LiB 10 Cl 10 , LiAlCl 4 , LiCl, LiBr, LiB (C 2 H 5 ) 4 , LiCF 3 SO 3 , LiCH 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 N, lithium of lower fatty acid carboxylate etc.
- an aqueous potassium hydroxide solution having a conventionally known concentration of 5 mol / liter or more can be used.
- the solvent for dissolving the electrolyte is not particularly limited, but specific examples thereof include carbonate compounds such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate; Lactone compounds such as butyl lactone; ether compounds such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran; sulfoxide compounds such as dimethyl sulfoxide; One or more selected from these can be used.
- the concentration of the electrolyte in the electrolytic solution is preferably 0.5 to 3.0 mol / L, more preferably 0.7 to 2.0 mol / L.
- an electricity storage device includes a positive electrode, a negative electrode, a protective film disposed between the positive electrode and the negative electrode, and an electrolytic solution, and the protective film Is the above-mentioned protective film.
- FIG. 13 is a schematic diagram illustrating a cross section of an electricity storage device according to a first specific example.
- the positive electrode 30 having the positive electrode active material layer 34 formed on the surface of the positive electrode current collector 32 and the negative electrode active material layer 44 formed on the surface of the negative electrode current collector 42.
- no separator is provided between the positive electrode 30 and the negative electrode 40. This is because if the positive electrode 30 and the negative electrode 40 are completely fixed with a solid electrolyte or the like, the positive electrode 30 and the negative electrode 40 will not contact and short-circuit.
- the positive electrode 30 shown in FIG. 13 is formed such that the positive electrode active material layer 34 is not provided on one surface along the longitudinal direction and the positive electrode current collector 32 is exposed, but the positive electrode active material is formed on both surfaces. A layer 34 may be provided.
- the negative electrode 40 shown in FIG. 13 is formed such that the negative electrode active material layer 44 is not provided on one surface along the longitudinal direction and the negative electrode current collector 42 is exposed, A negative electrode active material layer 44 may be provided.
- the materials described in “2.1. Active material” can be used as necessary.
- the materials described in “3. Electric storage device electrode” can be used as necessary.
- the positive electrode active material layer 34 and the negative electrode active material layer 44 can be manufactured as necessary under the conditions described in “3. Power storage device electrode”.
- the protective film 50 can be formed, for example, by applying the above-described slurry for forming a protective film on the surface of the positive electrode 30 (or the negative electrode 40) and drying it.
- a method for applying the protective film-forming slurry to the surface of the positive electrode 30 (or the negative electrode 40) it can be manufactured under the conditions described in the above-mentioned "5. Protective film”.
- the protective film 50 is disposed between the positive electrode 30 and the negative electrode 40.
- the protective film 50 is disposed between the positive electrode 30 and the negative electrode 40 so as to be in contact with the positive electrode active material layer 34, but is disposed so as to be in contact with the negative electrode active material layer 44. May be.
- the protective film 50 may be disposed as a self-supporting film between the positive electrode 30 and the negative electrode 40 without being in contact with the positive electrode 30 or the negative electrode 40. Thereby, even if it is a case where dendrites precipitate by repeating charging / discharging, since it is guarded by the protective film 50, a short circuit does not occur. Therefore, the function as an electricity storage device can be maintained.
- the thickness of the protective film 50 is not particularly limited, but is preferably in the range of 0.5 to 4 ⁇ m, and more preferably in the range of 0.5 to 3 ⁇ m. When the thickness of the protective film 50 is within the above range, the permeability of the electrolytic solution into the electrode and the liquid retaining property are improved, and an increase in the internal resistance of the electrode can be suppressed.
- the electrolytic solution 60 is appropriately selected and used according to the type of the target electricity storage device.
- As the electrolytic solution 60 a solution in which an appropriate electrolyte is dissolved in a solvent is used.
- the type and concentration of the electrolyte in the case of manufacturing a lithium ion capacitor are the same as in the case of the lithium ion secondary battery.
- FIG. 14 is a schematic diagram illustrating a cross section of an electricity storage device according to a second specific example.
- the positive electrode 130 in which the positive electrode active material layer 134 is formed on the surface of the positive electrode current collector 132 and the negative electrode active material layer 144 in the surface of the negative electrode current collector 142 are formed.
- the electricity storage device 200 is different from the electricity storage device 100 described above in that the protective film 150 is disposed between the positive electrode 130 and the separator 170.
- the protective film 150 is disposed so as to be sandwiched between the positive electrode 130 and the separator 170, but the protective film 150 is sandwiched between the negative electrode 140 and the separator 170. It may be arranged so that. By adopting such a configuration, even when dendrites are deposited by repeated charge and discharge, the protective film 150 guards the short circuit. Therefore, the function as an electricity storage device can be maintained.
- the protective film 150 can be formed, for example, by applying the above-described protective film-forming slurry to the surface of the positive electrode 130 (or the negative electrode 140) or the separator 170 and drying it. As a method of applying the protective film-forming slurry to the surface of the positive electrode 130 (or the negative electrode 140) or the separator 170, it can be manufactured under the conditions described in the above section “5.
- Any separator 170 may be used as long as it is electrically stable, chemically stable with respect to the positive electrode active material, the negative electrode active material, or the solvent, and has no electrical conductivity.
- a polymer nonwoven fabric, a porous film, glass or ceramic fibers in a paper shape can be used, and a plurality of these may be laminated.
- a porous polyolefin film is preferably used, and a composite of this with a heat-resistant material made of polyimide, glass, ceramic fibers or the like may be used.
- FIG. 15 is a schematic diagram illustrating a cross section of an electricity storage device according to a third specific example.
- the positive electrode 230 in which the positive electrode active material layer 234 is formed on the surface of the positive electrode current collector 232 and the negative electrode active material layer 244 is formed on the surface of the negative electrode current collector 242.
- the electricity storage device 300 is different from the electricity storage device 100 and the electricity storage device 200 described above in that the protective film 250 is formed so as to cover the surface of the separator 270.
- the protective film 250 guards and no short circuit occurs. Therefore, the function as an electricity storage device can be maintained.
- the protective film 250 can be formed, for example, by applying the above-described protective film-forming slurry to the surface of the separator 270 and drying it. As a method of applying the protective film-forming slurry to the surface of the separator 270, the separator 270 can be manufactured under the conditions described in "5. Protective film”.
- the shape of the battery can be an appropriate shape such as a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, or a flat shape.
- the power storage device as described above is suitable as a secondary battery or a capacitor mounted on an automobile such as an electric vehicle, a hybrid car, or a truck, and a secondary battery used for an AV device, an OA device, a communication device, or the like. It is also suitable as a capacitor.
- the binder composition for an electricity storage device of Examples 1 to 3 and Comparative Examples 1 to 5 is a binder composition for an electricity storage device for producing a positive electrode
- the binder composition for an electricity storage device of Examples 4 and 5 is: It was set as the binder composition for electrical storage devices for producing a negative electrode.
- the binder composition for an electricity storage device of Examples 6 to 10 and Comparative Examples 6 to 12 was a binder composition for an electricity storage device for forming a protective film.
- Example 1 7.1.1. Preparation of binder composition for electricity storage device After the inside of an autoclave having an internal volume of about 6 L equipped with an electromagnetic stirrer was sufficiently purged with nitrogen, 2.5 L of deoxygenated pure water and 25 g of ammonium perfluorodecanoate were charged as an emulsifier. The temperature was raised to 60 ° C. while stirring at 350 rpm. Next, a mixed gas composed of 70% of vinylidene fluoride (VDF) as a monomer and 30% of propylene hexafluoride (HFP) was charged until the internal pressure reached 20 kg / cm 2 .
- VDF vinylidene fluoride
- HFP propylene hexafluoride
- the particle size distribution was measured using a particle size distribution measuring apparatus (manufactured by Otsuka Electronics Co., Ltd., type “FPAR-1000”) based on the dynamic light scattering method.
- the number average particle diameter (Da) was determined from the particle size distribution to be 330 nm.
- the major axis (Rmax) and minor axis (Rmin) of ten polymer particles were measured with a transmission electron microscope (manufactured by Hitachi High-Technologies Corporation, model “H-7650”), and the average value was calculated.
- the major axis was 360 nm
- the minor axis was 300 nm
- the ratio of the major axis to the minor axis (Rmax / Rmin) was 1.20.
- the spinnability in the slurry for the electricity storage device electrode is good when it is 30 to 80%.
- the crack rate is preferably 0%, but when the electrode plate group is manufactured by winding the electrode in a spiral shape through a separator, the crack rate is allowed up to 20%. However, if the crack rate is greater than 20%, the electrodes are easily cut off, making it impossible to manufacture the electrode plate group, and the productivity of the electrode plate group decreases. From this, it is considered that a good range is up to 20% as the threshold of the crack rate.
- the measurement results of the crack rate are also shown in Table 1.
- the obtained slurry for the counter electrode (negative electrode) is uniformly applied to the surface of the current collector made of copper foil by a doctor blade method so that the film thickness after drying is 150 ⁇ m, and dried at 120 ° C. for 20 minutes. did.
- the counter electrode (negative electrode) was obtained by pressing using a roll-press machine so that the density of a film
- a lithium ion battery cell (power storage device) was assembled by placing the positive electrode manufactured in the above-described method by punching and molding the positive electrode to a diameter of 16.16 mm, and sealing the outer body of the bipolar coin cell with a screw.
- charging is started at a constant current (3C) for the same cell, and when the voltage reaches 4.2V, charging is continued at a constant voltage (4.2V).
- the charging capacity at 3C was measured with the time point of becoming the completion of charging (cut-off).
- discharge was started at a constant current (3C), and when the voltage reached 2.7 V, the discharge was completed (cut off), and the discharge capacity at 3C was measured.
- the discharge rate (%) was calculated by calculating the ratio (percentage%) of the discharge capacity at 3C to the discharge capacity at 0.2C using the above measured value. When the discharge rate is 80% or more, it can be evaluated that the discharge rate characteristics are good. The measured discharge rate values are also shown in Table 1.
- 1C in the measurement condition indicates a current value at which discharge is completed in one hour after constant-current discharge of a cell having a certain electric capacity.
- 0.1 C is a current value at which discharge is completed over 10 hours
- 10 C is a current value at which discharge is completed over 0.1 hours.
- Example 2 and Comparative Example 3 7.2.1. Preparation of Binder Composition for Electricity Storage Device Example 1 except that the composition of the monomer and the amount of the emulsifier were appropriately changed in “7.1.1. Preparation of Binder Composition for Electricity Storage Device” in Example 1 above. Similarly, an aqueous dispersion containing polymer particles having the composition shown in Table 1 is prepared, and water is removed under reduced pressure or added according to the solid content concentration of the aqueous dispersion, so that the solid content concentration is 40%. An aqueous dispersion was obtained. The number average particle diameter measurement, the ratio calculation result of the major axis and minor axis, and DSC measurement were performed in the same manner as in Example 1 for the obtained polymer particles. The results are also shown in Table 1.
- Example 3 7.3.1. Preparation of Binder Composition for Electricity Storage Device Example 1 except that the composition of the monomer gas and the amount of emulsifier were changed appropriately in “7.1.1. Preparation of Binder Composition for Electricity Storage Device” in Example 1 above.
- an aqueous dispersion containing polymer particles having the composition shown in Table 1 was prepared, and water was removed under reduced pressure or added in accordance with the solid content concentration of the aqueous dispersion to obtain a solid content concentration of 40%. An aqueous dispersion was obtained.
- NMP N-methylpyrrolidone
- Example 3 Preparation of slurry for power storage device electrode
- active material particles (LiFePO 4 ) having a number average particle diameter (Db) of 3 ⁇ m obtained above were used.
- a biaxial planetary mixer product name “TK Hibismix 2P-03” manufactured by PRIMIX Co., Ltd.
- a thickener product name “CMC2200” manufactured by Daicel Chemical Industries, Ltd.
- 3 parts (solid content conversion) 100 parts of active material particles having a number average particle diameter of 3 ⁇ m, 5 parts of acetylene black, 4 parts of the binder composition for an electricity storage device prepared above (in terms of solid content) and 68 parts of NMP were added, and 2 hours at 60 rpm.
- the paste was obtained by stirring.
- Comparative Example 1 7.4.1. Preparation of Binder Composition for Electricity Storage Device After the inside of a 7 L capacity separable flask was sufficiently purged with nitrogen, an emulsifier “ADEKA rear soap SR1025” (trade name, manufactured by ADEKA Corporation) 0.5 part, styrene (ST) 25 Of water, 5 parts of butadiene (BD) and 130 parts of water were added sequentially, and then 20 mL of a tetrahydrofuran solution containing 0.5 part of azobisisobutyronitrile as an oil-soluble polymerization initiator was added, and the temperature was raised to 75 ° C. The reaction was carried out for 3 hours and further at 85 ° C. for 2 hours. After adding 20 parts of glycidyl methacrylate (GMA) to the reaction solution and continuing the reaction for 3 hours, the reaction solution was cooled and simultaneously stirred to obtain an aqueous dispersion containing 40% of polymer particles.
- GMA glycidyl
- the monomer component was absorbed into the polymer particles by stirring slowly. Then, it heated up at 75 degreeC and reacted for 3 hours, and also reacted at 85 degreeC for 2 hours. Then, after cooling, the reaction was stopped, and the aqueous dispersion (binder composition) containing 40% polymer particles was obtained by adjusting the pH to 7 with a 2.5N aqueous sodium hydroxide solution.
- the number average particle diameter measurement performed on the obtained polymer particles, the ratio calculation result of the major axis and minor axis, and DSC measurement were performed in the same manner as in Example 1. The results are also shown in Table 1.
- Lithium iron phosphate (LiFePO 4 ) having a number average particle diameter (Db) of 7 ⁇ m obtained above was used as active material particles, and the types and amounts of thickening described in Table 1 were used. Except for using the agent, an electrode (positive electrode) slurry was prepared in the same manner as in “7.1.2. Preparation of electricity storage device electrode slurry” in Example 1, and the spinnability was measured. The value of the spinnability is also shown in Table 1.
- Example 4 7.6.1. Preparation of Binder Composition for Electricity Storage Device Example 1 except that the composition of the monomer and the amount of the emulsifier were appropriately changed in “7.1.1. Preparation of Binder Composition for Electricity Storage Device” in Example 1 above. Similarly, an aqueous dispersion containing polymer particles having the composition shown in Table 1 is prepared, and water is removed under reduced pressure or added according to the solid content concentration of the aqueous dispersion, so that the solid content concentration is 40%. An aqueous dispersion was obtained. The number average particle diameter measurement, the ratio calculation result of the major axis and minor axis, and DSC measurement were performed in the same manner as in Example 1 for the obtained polymer particles. The results are also shown in Table 1.
- the slurry for positive electrode was prepared by stirring and mixing for 5 minutes at 1800 rpm for 1 minute at 1800 rpm.
- the obtained positive electrode slurry was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 80 ⁇ m, followed by drying treatment at 120 ° C. for 20 minutes.
- the positive electrode for secondary batteries was obtained by pressing with a roll press so that the density of an electrode layer may be 3.0 g / cm ⁇ 3 >.
- Example 5 7.7.1. Preparation of Binder Composition for Electricity Storage Device
- “7.6.1. Preparation of Binder Composition for Electricity Storage Device” in Example 4 above the composition of the monomer and the amount of the emulsifier were changed as appropriate, and graphite was used.
- the number average particle diameter measurement, the ratio calculation result of the major axis and minor axis, and DSC measurement were performed in the same manner as in Example 1 for the obtained polymer particles. The results are also shown in Table 1.
- CMC1120, CMC1150, CMC2200, CMC2280, and CMC2450 described in the thickener column are trade names of Daicel Chemical Industries, Ltd., and are alkali metal salts of carboxymethylcellulose.
- Example 6 7.8.1. Preparation of slurry for forming protective film Titanium oxide (product name “KR380”, manufactured by Titanium Industry Co., Ltd., rutile type, average number particle diameter 0.38 ⁇ m) as inorganic particles is 20 parts by mass with respect to 100 parts by mass of water. 5 parts by mass of the binder composition for an electricity storage device prepared in “7.1.1. Preparation of binder composition for an electricity storage device” in Example 1 in terms of solid content with respect to inorganic particles, a thickener (Daicel Chemical Co., Ltd.) Product, product name “CMC1120”) 1 part by mass, K. Using a Mixmix (R) 56-50 type (manufactured by PRIMIX Co., Ltd.), a mixture dispersion treatment was performed to prepare a slurry for forming a protective film in which titanium oxide was dispersed.
- a Mixmix (R) 56-50 type manufactured by PRIMIX Co., Ltd.
- Electrode and Electricity Storage Device After applying the protective film-forming slurry obtained above to the surface of the positive electrode active material layer of the positive electrode produced in Example 1 above using a die coating method, A protective film was formed on the surface of the positive electrode active material layer by drying for 5 minutes. The protective film had a thickness of 3 ⁇ m.
- a lithium ion battery cell was produced in the same manner as in Example 1 except that a positive electrode having a protective film formed on the surface of the positive electrode active material layer was used. However, when the positive electrode was mounted on the separator, the positive electrode was formed so that the surface on which the protective film of the positive electrode was formed and the separator faced each other.
- the cell after the aging charge / discharge is put in a thermostat at 25 ° C., and charging is started at a constant current (0.2 C).
- a constant current 0.2 C
- the cell is continuously maintained at a constant voltage (4.1 V).
- Charging was continued, and charging was completed (cut off) when the current value reached 0.01C.
- discharge was started at a constant current (0.2 C), and when the voltage reached 2.5 V, the discharge was completed (cut off), and C1 which was the value of the discharge capacity (initial) at 0.2 C was measured. did.
- EIS measurement (“Electrochemical Impedance Spectroscopy”, “electrochemical impedance measurement”) was performed on the charged cell, and the initial resistance value EISA was measured.
- the charged cell was placed in a constant temperature bath at 25 ° C., the cell temperature was lowered to 25 ° C., and then discharging was started at a constant current (0.2 C), and the voltage became 2.5V. Was completed (cutoff), and C2 as a value of the discharge capacity at 0.2 C (after the test) was measured.
- the cell having the above discharge capacity (after the test) is placed in a constant temperature bath at 25 ° C., and charging is started at a constant current (0.2 C).
- a constant current 0.2 C
- the charging was continued at, and the time when the current value reached 0.01 C was regarded as charging completion (cut-off).
- discharging was started at a constant current (0.2 C), and the time when the voltage reached 2.5 V was regarded as completion of discharging (cut-off).
- EIS measurement of this cell was performed, and EISb which is a resistance value after application of thermal stress and overcharge stress was measured.
- the residual capacity ratio obtained by substituting the above measured values into the following formula (5) is 80.5%, and the resistance increase rate obtained by substituting the above measured values into the following formula (6) is 210. %Met.
- Remaining capacity ratio (%) (C2 / C1) ⁇ 100 (5)
- Resistance increase rate (%) (EISb / EISa) ⁇ 100 (6)
- Examples 7 to 10, Comparative Example 6 to Comparative Example 10 An electricity storage device was produced and evaluated in the same manner as in Example 6 except that the binder composition for an electricity storage device used in Examples 2 to 5 and Comparative Examples 1 to 5 was used. The evaluation results are also shown in Table 2.
- the power storage device binder compositions of Examples 7 to 10 correspond to the power storage device binder compositions of Examples 2 to 5, respectively, and the power storage device binder compositions of Comparative Examples 6 to 10, respectively. This corresponds to the binder compositions for power storage devices of Comparative Examples 1 to 5, but in Examples 7 to 10 and Comparative Example 10, the type of liquid medium was changed to that shown in Table 2, respectively.
- the abbreviations of the components in Table 2 are the same as those in Table 1 except for the inorganic particles.
- the inorganic particles used are shown below.
- ⁇ Inorganic particles> -Titanium oxide The product name “KR380” (manufactured by Titanium Industry Co., Ltd., rutile type, number average particle size 0.38 ⁇ m) is used as it is, or the product name “KR380” is ground in an mortar and sieved. Thus, titanium oxide having a number average particle size of 0.08 ⁇ m and 0.12 ⁇ m was prepared and used.
- Aluminum oxide Product name “AKP-3000” (manufactured by Sumitomo Chemical Co., Ltd., number average particle size 0.74 ⁇ m), or product name “AKP-50” (manufactured by Sumitomo Chemical Co., Ltd., number average particle size 0.22 ⁇ m) was used.
- Zirconium oxide Product name “UEP zirconium oxide” (manufactured by Daiichi Elemental Chemical Co., Ltd., number average particle diameter 0.67 ⁇ m)
- Silica Product name “Seahoster (R) KE-S50” (manufactured by Nippon Shokubai Co., Ltd., number average particle size 0.54 ⁇ m), or product name “Seahoster (R) KE-S100” (manufactured by Nippon Shokubai Co., Ltd., number An average particle size of 0.98 ⁇ m) was used.
- Magnesium oxide Product name “PUREMAG® FNM-G” (manufactured by Tateho Chemical Co., Ltd., number average particle size 0.50 ⁇ m)
- the electricity storage device (lithium ion secondary battery) comprising the electricity storage device electrode having the protective film according to the present invention shown in Examples 6 to 10 is the residual after the initial resistance and durability test. It was excellent in capacity and suppression of resistance rise. On the other hand, in Comparative Examples 6 to 10, an electricity storage device that satisfies both good residual capacity and suppression of the rate of increase in resistance could not be obtained. When the binders of Comparative Examples 11 to 12 were used, the initial resistance of the electricity storage device was high, and the resistance increase rate of the electricity storage device after the durability test was poor.
- the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment.
- the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced.
- the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object.
- the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Separators (AREA)
Abstract
Description
本発明に係る蓄電デバイス用バインダー組成物の一態様は、
含フッ素化合物に由来する繰り返し単位(a)および多官能(メタ)アクリル酸エステルに由来する繰り返し単位(b)を含む重合体粒子(A)と、液状媒体(B)と、を含有する蓄電デバイス用バインダー組成物において、
前記重合体粒子(A)についてJIS K7121に準拠して示差走査熱量測定(DSC)を行ったときに、-30℃~30℃の温度範囲における吸熱ピークが一つおよび80℃~150℃の温度範囲における吸熱ピークが一つ観測されることを特徴とする。
適用例1の蓄電デバイス用バインダー組成物において、
前記重合体粒子(A)中における、前記繰り返し単位(a)と前記繰り返し単位(b)との量比が質量基準で2:1~10:1の範囲にあることができる。
適用例1または適用例2の蓄電デバイス用バインダー組成物において、
前記重合体粒子(A)の数平均粒子径が50~400nmの範囲にあることができる。
適用例1ないし適用例3のいずれか一例の蓄電デバイス用バインダー組成物において、
前記重合体粒子(A)の長径(Rmax)と短径(Rmin)との比率(Rmax/Rmin)が1.1~1.5の範囲にあることができる。
適用例1ないし適用例4のいずれか一例の蓄電デバイス用バインダー組成物において、
前記重合体粒子(A)が、不飽和カルボン酸に由来する繰り返し単位(c)をさらに含み、該重合体粒子(A)100質量部に対して、前記含フッ素化合物に由来する繰り返し単位(a)5~50質量部と、前記不飽和カルボン酸に由来する繰り返し単位(c)1~10質量部と、を含有することができる。
適用例1ないし適用例5のいずれか一例の蓄電デバイス用バインダー組成物は、
蓄電デバイスの正極を作製する用途に用いることができる。
本発明に係る蓄電デバイス電極用スラリーの一態様は、
適用例1ないし適用例6のいずれか一例の蓄電デバイス用バインダー組成物と、活物質と、を含有することを特徴とする。
本発明に係る蓄電デバイス電極の一態様は、
集電体と、前記集電体の表面に適用例7の蓄電デバイス電極用スラリーを塗布、乾燥して作製された活物質層と、を備えることを特徴とする。
本発明に係る保護膜形成用スラリーの一態様は、
適用例1ないし適用例5のいずれか一例の蓄電デバイス用バインダー組成物と、無機粒子と、を含有することを特徴とする。
適用例9の保護膜形成用スラリーにおいて、
前記無機粒子が、シリカ、酸化チタン、酸化アルミニウム、酸化ジルコニウムおよび酸化マグネシウムよりなる群から選択される少なくとも1種の粒子であることができる。
本発明に係る保護膜の一態様は、
適用例9または適用例10の保護膜形成用スラリーを用いて作製されることを特徴とする。
本発明に係る蓄電デバイスの一態様は、
適用例8の蓄電デバイス電極を備えることを特徴とする。
本発明に係る蓄電デバイスの一態様は、
適用例11の保護膜を備えることを特徴とする。
適用例13の蓄電デバイスにおいて、
正極と、負極と、をさらに備え、前記保護膜が前記正極および前記負極の少なくとも一方の表面と接してなることができる。
適用例14の蓄電デバイスにおいて、
前記正極および前記負極の間に配置されたセパレータをさらに備えることができる。
適用例13の蓄電デバイスにおいて、
正極と、負極と、前記正極および前記負極の間に配置されたセパレータと、をさらに備え、前記セパレータの表面が前記保護膜によって被覆されることができる。
本実施の形態に係る蓄電デバイス用バインダー組成物は、含フッ素化合物に由来する繰り返し単位(a)および多官能(メタ)アクリル酸エステルに由来する繰り返し単位(b)を含む重合体粒子(A)と、液状媒体(B)と、を含有し、前記重合体粒子(A)についてJIS K7121に準拠して示差走査熱量測定(DSC)を行ったときに、-30℃~30℃の温度範囲における吸熱ピークが一つおよび80℃~150℃の温度範囲における吸熱ピークが一つ観測されることを特徴とする。本実施の形態に係る蓄電デバイス用バインダー組成物は、重合体粒子(A)が液状媒体(B)中に分散されたラテックスの状態で存在するものである。
1.1.1.重合体粒子(A)の形状および大きさ
本実施の形態に係る蓄電デバイス用バインダー組成物に含有される重合体粒子(A)は、数平均粒子径(Da)が50~400nmの範囲にあることが好ましく、100~250nmの範囲にあることがより好ましい。重合体粒子(A)の数平均粒子径が前記範囲にあると、後述するような活物質粒子や無機粒子の表面に重合体粒子が十分に吸着することができるため、活物質粒子や無機粒子の移動に伴って重合体粒子も追随して移動することができる。その結果、粒子のうちのどちらかのみが単独でマイグレーションすることを抑制できるため、電気的特性の劣化を低減させることができる。
本実施の形態に係る蓄電デバイス用バインダー組成物は、含フッ素化合物に由来する繰り返し単位(a)および多官能(メタ)アクリル酸エステルに由来する繰り返し単位(b)を含有する重合体粒子(A)を含む。以下、重合体粒子(A)を構成する繰り返し単位について説明する。
重合体粒子(A)は、含フッ素化合物に由来する繰り返し単位(a)を含有する。含フッ素化合物に由来する繰り返し単位(a)は、エチレン性不飽和結合を有する含フッ素化合物に由来する繰り返し単位(a)であることが好ましい。エチレン性不飽和結合を有する含フッ素化合物としては、例えばフッ素原子を有するオレフィン化合物、フッ素原子を有する(メタ)アクリル酸エステル等が挙げられる。フッ素原子を有するオレフィン化合物としては、例えばフッ化ビニリデン、四フッ化エチレン、六フッ化プロピレン、三フッ化塩化エチレン、パーフルオロアルキルビニルエーテル等が挙げられる。フッ素原子を有する(メタ)アクリル酸エステルとしては、例えば下記一般式(1)で表される化合物、(メタ)アクリル酸3[4[1-トリフルオロメチル-2,2-ビス[ビス(トリフルオロメチル)フルオロメチル]エチニルオキシ]ベンゾオキシ]2-ヒドロキシプロピル等が挙げられる。
重合体粒子(A)は、多官能(メタ)アクリル酸エステルに由来する繰り返し単位(b)を含有する。重合体粒子(A)が繰り返し単位(b)を含有することにより、上述したような異形粒子を作製することが容易となる。すなわち、上述した図4~図9に示される異形粒子の例によれば、シード粒子となる第1の重合体粒子の表面及び/又は内部に存在する繰り返し単位(b)が起点ないし契機となることによって、第2の重合体粒子が形成されるのである。その生成メカニズムについては、後に詳述する。
重合体粒子(A)は、不飽和カルボン酸に由来する繰り返し単位(c)をさらに含有するものであることが好ましい。重合体粒子(A)が不飽和カルボン酸に由来する構成単位(c)を有することにより、本実施の形態に係る蓄電デバイス用バインダー組成物を用いた蓄電デバイス電極用スラリーおよび保護膜形成用スラリー(以下、これらを総括して単に「スラリー」ともいう。)の安定性が向上する。
重合体粒子(A)は、単官能(メタ)アクリル酸エステルに由来する繰り返し単位(d)をさらに含有するものであることが好ましい。重合体粒子(A)が単官能(メタ)アクリル酸エステル化合物に由来する繰り返し単位(d)を有することにより、得られる重合体粒子(A)は、電解液との親和性が適度なものとなり、蓄電デバイス中でバインダーが電気抵抗成分となることによる内部抵抗の上昇を抑制すると共に、電解液を過大に吸収することによる密着性の低下を防ぐことができる。
重合体粒子(A)は、α,β-不飽和ニトリル化合物に由来する繰り返し単位(e)をさらに含有するものであることが好ましい。重合体粒子(A)が繰り返し単位(e)を有することにより、重合体粒子(A)の電解液に対する膨潤性をより向上させることができる。すなわち、ニトリル基の存在によって重合体鎖からなる網目構造に溶媒が侵入し易くなって網目間隔が広がるため、溶媒和したリチウムイオンがこの網目構造をすり抜けて移動し易くなる。これにより、リチウムイオンの拡散性が向上すると考えられ、その結果、電極抵抗が低下してより良好な充放電特性を実現することができるのである。
重合体粒子(A)は、共役ジエン化合物に由来する繰り返し単位(f)をさらに含有してもよい。共役ジエン化合物の具体例としては、1,3-ブタジエン、2-メチル-1,3-ブタジエン、2,3-ジメチル-1,3-ブタジエン、2-クロル-1,3-ブタジエンなどを挙げることができ、これらのうちから選択される1種以上であることができる。重合体粒子(A)における繰り返し単位(f)の含有割合は、重合体粒子(A)100質量部に対して、35質量部以下であることができる。
重合体粒子(A)は、芳香族ビニル化合物に由来する繰り返し単位(g)をさらに含有してもよい。芳香族ビニル化合物の具体例としては、例えばスチレン、α-メチルスチレン、p-メチルスチレン、ビニルトルエン、クロルスチレン、ジビニルベンゼンなどを挙げることができる。重合体粒子(A)における繰り返し単位(g)の含有割合は、重合体粒子(A)100質量部に対して、50質量部以下であることができる。
重合体粒子(A)は、必要に応じて上記以外の化合物に由来する繰り返し単位をさらに含有してもよい。その他の化合物の具体例としては、例えば(メタ)アクリルアミド、N-メチロールアクリルアミド等のエチレン性不飽和カルボン酸のアルキルアミド;酢酸ビニル、プロピオン酸ビニル等のカルボン酸ビニルエステル;エチレン性不飽和ジカルボン酸の酸無水物;アミノエチルアクリルアミド、ジメチルアミノメチルメタクリルアミド、メチルアミノプロピルメタクリルアミド等のエチレン性不飽和カルボン酸のアミノアルキルアミドを挙げることができ、これらのうちから選択される1種以上であることができる。
1.1.3.1.重合体粒子(A)の熱特性
上述したような重合体粒子(A)をJIS K7121に準拠する示差走査熱量測定(DSC)によって測定した場合、-30℃~30℃の温度範囲における吸熱ピークが1つおよび80℃~150℃の温度範囲における吸熱ピークが1つ観測される。このように吸熱ピークが2つ観測された場合、重合体粒子(A)には少なくとも2つの転移温度が存在することが理解される。重合体粒子(A)の有する吸熱ピークの1つの温度が-30~+30℃の範囲にあると、電極用バインダー組成物として使用する場合には、該粒子は活物質層に対してより良好な柔軟性と粘着性とを付与することができ、従って密着性をより向上させることができる。一方、保護膜形成用バインダー組成物として使用する場合には、該粒子は保護膜により良好な柔軟性と粘着性とを付与することができ、従って密着性をより向上させることができる。
重合体粒子(A)のTHF不溶分は、80%以上であることが好ましく、90%以上であることがより好ましい。THF不溶分は、蓄電デバイスで使用する電解液への不溶分量とほぼ比例すると推測される。このため、THF不溶分が前記範囲であれば、蓄電デバイスを作製して、長期間にわたり充放電を繰り返した場合でも電解液への重合体粒子(A)の溶出を抑制できる。
本実施の形態に係る蓄電デバイス用バインダー組成物に含まれる重合体粒子(A)は、上記のような構成をとるものである限り、その合成方法は特に限定されないが、例えば公知の乳化重合工程またはこれを適宜に組み合わせることによって、容易に合成することができる。例えば、特開2007-197588号公報に記載の方法により作製することができる。
本実施の形態に係る蓄電デバイス用バインダー組成物は、液状媒体(B)を含有する。上記液状媒体(B)は、水を含有する水系媒体であることが好ましい。この水系媒体は、水以外に少量の非水系媒体を含有することができる。このような非水系媒体としては、例えばアミド化合物、炭化水素、アルコール、ケトン、エステル、アミン化合物、ラクトン、スルホキシド、スルホン化合物等を挙げることができ、これらのうちから選択される1種以上を使用することができる。このような非水系媒体の含有割合は、水系媒体100質量部に対して10質量部以下であることが好ましく、5質量部以下であることがより好ましく、非水系媒体を含有せずに水のみからなるものであることが最も好ましい。
本実施の形態に係る蓄電デバイス用バインダー組成物は、上述する重合体粒子(A)、液状媒体(B)の他に、必要に応じてその他の添加剤をさらに含有させることができる。たとえば、その塗布性や蓄電デバイスの充放電特性等をさらに向上させる観点から、増粘剤を含有させることができる。
前述の蓄電デバイス用バインダー組成物を用いて、本実施の形態に係る蓄電デバイス電極用スラリーを製造することができる。蓄電デバイス電極用スラリーとは、これを集電体の表面に塗布した後、乾燥して、集電体表面上に活物質層を形成するために用いられる分散液のことをいう。本実施の形態に係る蓄電デバイス電極用スラリーは、前述の蓄電デバイス用バインダー組成物と、活物質と、水と、を含有する。以下、本実施の形態に係る蓄電デバイス電極用スラリーに含まれる成分についてそれぞれ詳細に説明する。ただし、蓄電デバイス用バインダー組成物に含まれる成分については、前述した通りであるから省略する。
蓄電デバイス電極用スラリーに含まれる活物質を構成する材料としては特に制限はなく、目的とする蓄電デバイスの種類により適宜適当な材料を選択することができる。
Li1-xMx(XO4) ・・・・・(2)
(式中、Mは、Mg、Ti、V、Nb、Ta、Cr、Mn、Fe、Co、Ni、Cu、Zn、Al、Ga、GeおよびSnよりなる群から選択される金属のイオンの少なくとも1種であり;Xは、Si、S、PおよびVよりなる群から選択される少なくとも1種であり;xは数であり、Mおよび(XO4)の価数に応じて、式(2)全体の価数が0価となるように選択され、0<x<1の関係を満たす。)
上記蓄電デバイス電極用スラリーは、必要に応じて前述した成分以外の成分を含有することができる。このような成分としては、例えば導電付与剤、非水系媒体、増粘剤等が挙げられる。
上記導電付与剤の具体例としては、リチウムイオン二次電池においてはカーボンなどが;ニッケル水素二次電池においては、正極では酸化コバルトが:負極ではニッケル粉末、酸化コバルト、酸化チタン、カーボンなどが、それぞれ用いられる。上記両電池において、カーボンとしては、グラファイト、活性炭、アセチレンブラック、ファーネスブラック、黒鉛、炭素繊維、フラーレンなどを挙げることができる。これらの中でも、アセチレンブラックまたはファーネスブラックを好ましく使用することができる。導電付与剤の使用割合は、活物質100質量部に対して、好ましくは20質量部以下であり、より好ましくは1~15質量部であり、特に好ましくは2~10質量部である。
上記蓄電デバイス電極用スラリーは、その塗布性を改善する観点から、80~350℃の標準沸点を有する非水系媒体を含有することができる。このような非水系媒体の具体例としては、例えばN-メチルピロリドン、ジメチルホルムアミド、N,N-ジメチルアセトアミドなどのアミド化合物;トルエン、キシレン、n-ドデカン、テトラリン等の炭化水素;2-エチル-1-ヘキサノール、1-ノナノール、ラウリルアルコール等のアルコール;メチルエチルケトン、シクロヘキサノン、ホロン、アセトフェノン、イソホロン等のケトン;酢酸ベンジル、酪酸イソペンチル、乳酸メチル、乳酸エチル、乳酸ブチル等のエステル;o-トルイジン、m-トルイジン、p-トルイジン等のアミン化合物;γ-ブチロラクトン、δ-ブチロラクトン等のラクトン;ジメチルスルホキシド、スルホラン等のスルホキシド・スルホン化合物等を挙げることができ、これらのうちから選択される1種以上を使用することができる。これらの中でも、重合体粒子の安定性や蓄電デバイス電極用スラリーを塗布する際の作業性等の点から、N-メチルピロリドンを使用することが好ましい。
上記蓄電デバイス電極用スラリーは、その塗工性を改善する観点から、増粘剤を含有することができる。増粘剤の具体例としては、前記「1.3.その他の添加剤」に記載した各種化合物が挙げられる。
本実施の形態に係る蓄電デバイス電極用スラリーは、前述の蓄電デバイス用バインダー組成物と、活物質と、水と、必要に応じて用いられる添加剤と、を混合することにより製造することができる。これらの混合には公知の手法による攪拌によって行うことができ、例えば攪拌機、脱泡機、ビーズミル、高圧ホモジナイザー等を利用することができる。
前述の蓄電デバイス用バインダー組成物に含まれる重合体粒子(A)の数平均粒子径(Da)と活物質の数平均粒子径(Db)との比(Da/Db)は、0.01~1.0の範囲にあることが好ましく、0.05~0.5の範囲にあることがより好ましい。このことの技術的な意味は、以下の通りである。
まず、底部に直径5.2mmの開口部を有するザーンカップ(太佑機材株式会社製、ザーンビスコシティーカップNo.5)を準備する。この開口部を閉じた状態で、ザーンカップに蓄電デバイス電極用スラリー40gを流し込む。その後、開口部を開放すると、開口部から蓄電デバイス電極用スラリーが流れ出す。ここで、開口部を開放した時をT0、蓄電デバイス電極用スラリーの曳糸が終了した時をTA、蓄電デバイス電極用スラリーの流出が終了した時をTBとした場合に、本明細書における「曳糸性」は下記数式(3)から求めることができる。
曳糸性(%)=((TA-T0)/(TB-T0))×100 ・・・・・(3)
本実施の形態に係る蓄電デバイス電極は、集電体と、前記集電体の表面上に前述の蓄電デバイス電極用スラリーが塗布、乾燥されて形成された層と、を備えるものである。かかる蓄電デバイス電極は、金属箔などの適宜の集電体の表面に、前述の蓄電デバイス電極用スラリーを塗布して塗膜を形成し、次いで該塗膜を乾燥することにより製造することができる。このようにして製造された蓄電デバイス電極は、集電体上に、前述の重合体粒子(A)および活物質、さらに必要に応じて添加した任意成分を含有する活物質層が結着されてなるものである。かかる蓄電デバイス電極は、集電体と活物質層との密着性に優れるとともに、電気的特性の一つである充放電レート特性が良好である。
本実施の形態に係る保護膜形成用スラリーは、上述した蓄電デバイス用バインダー組成物(保護膜形成用バインダー組成物)と、無機粒子と、を含有する。保護膜形成用スラリーとは、これを電極またはセパレータの表面もしくはその両方に塗布した後、乾燥させて、電極またはセパレータの表面もしくはその両方に保護膜を形成するために用いられる分散液である。
本実施の形態に係る保護膜形成用スラリーは、無機粒子を含有することにより、形成される保護膜のタフネスを向上させることができる。
本実施の形態に係る保護膜形成用スラリーは、必要に応じて、導電付与剤、水、非水系媒体、増粘剤、界面活性剤等のその他の成分を含有することができる。
導電付与剤としては、前記「2.2.1.導電付与剤」に記載されている材料、添加量を必要に応じて用いることができる。
本実施の形態に係る保護膜形成用スラリーは、水を含有することができる。水を含有することにより、保護膜形成用スラリーの安定性が良好となり、保護膜を再現性よく製造することが可能となる。水は、一般的に使用されている高沸点溶剤(例えば、N-メチルピロリドン等)と比較して蒸発速度が速く、溶媒除去時間の短縮による生産性の向上、粒子のマイグレーションの抑制等の効果が期待できる。
非水系媒体としては、前記「2.2.2.非水系媒体」に記載されている材料、添加量を必要に応じて用いることができる。これらの中でも、蓄電デバイス用バインダー組成物が液状媒体として水を含有するものである場合は水と混和するものが好ましい。
増粘剤としては、前記「1.3.その他の添加剤」に記載した各種化合物が挙げられる。保護膜形成用スラリーが増粘剤を含有する場合、増粘剤の使用割合としては、蓄電デバイス電極用スラリーの全固形分量に対して、好ましくは20質量%以下であり、より好ましくは0.1~15質量%であり、特に好ましくは0.5~10質量%である。
本実施の形態に係る保護膜形成用スラリーは、その分散性および分散安定性を改善する観点から界面活性剤を含有することができる。界面活性剤としては、前記「1.1.4.重合体粒子(A)の作製方法」に記載されているものが挙げられる。
本実施の形態に係る保護膜形成用スラリーは、無機粒子100質量部に対して、上述の蓄電デバイス用バインダー組成物が、固形分換算で0.1~20質量部含有されていることが好ましく、1~10質量部含有されていることがより好ましい。蓄電デバイス用バインダー組成物の含有割合が固形分換算で0.1~10質量部であることにより、形成される保護膜のタフネスとリチウムイオンの透過性とのバランスが良好となり、その結果、得られる蓄電デバイスの抵抗上昇率をより低くすることができる。
本実施の形態に係る保護膜は、正極、負極またはセパレータの表面に、前述した保護膜形成用スラリーを塗布して乾燥させることにより形成することができる。
6.1.第1の実施形態
本発明の一実施形態に係る蓄電デバイスは、上述した蓄電デバイス電極を備え、さらに電解液を含有し、セパレータなどの部品を用いて、常法に従って製造することができる。具体的な製造方法としては、例えば、負極と正極とをセパレータを介して重ね合わせ、これを電池形状に応じて巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口する方法が挙げられる。電池の形状は、コイン型、ボタン型、シート型、円筒型、角形、扁平型など、適宜の形状であることができる。
また、本発明の一実施形態に係る蓄電デバイスは、正極と、負極と、前記正極および前記負極の間に配置された保護膜と、電解液と、を備え、前記保護膜が上述の保護膜であることを特徴とする。以下、具体例について図面を参照しながら説明する。
図13は、第1の具体例に係る蓄電デバイスの断面を示した模式図である。図13に示すように、蓄電デバイス100は、正極集電体32の表面に正極活物質層34が形成された正極30と、負極集電体42の表面に負極活物質層44が形成された負極40と、正極30と負極40との間に設けられた保護膜50と、正極10と負極20の間を満たす電解液60と、を備えたものである。なお、蓄電デバイス100では、正極30と負極40との間にセパレータが設けられていない。正極30と負極40とが固体電解質等で完全に固定されていれば、正極30と負極40とが接触して短絡することはないからである。
図14は、第2の具体例に係る蓄電デバイスの断面を示した模式図である。図14に示すように、蓄電デバイス200は、正極集電体132の表面に正極活物質層134が形成された正極130と、負極集電体142の表面に負極活物質層144が形成された負極140と、正極130と負極140との間に設けられた保護膜150と、正極130と負極140の間を満たす電解液160と、正極130と負極140との間に設けられたセパレータ170と、を備えたものである。
図15は、第3の具体例に係る蓄電デバイスの断面を示した模式図である。図15に示すように、蓄電デバイス300は、正極集電体232の表面に正極活物質層234が形成された正極230と、負極集電体242の表面に負極活物質層244が形成された負極240と、正極230と負極240の間を満たす電解液260と、正極230と負極240との間に設けられたセパレータ270と、セパレータ270の表面を覆うようにして形成された保護膜250と、を備えたものである。
上述したような第2の実施形態に係る蓄電デバイスの製造方法としては、例えば、2つの電極(正極および負極の2つ、またはキャパシタ用電極の2つ)を必要に応じてセパレータを介して重ね合わせ、これを電池形状に応じて巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口する方法が挙げられる。電池の形状は、コイン型、ボタン型、シート型、円筒型、角形、扁平型など、適宜の形状であることができる。
上述したような蓄電デバイスは、電気自動車、バイブリッドカー、トラック等の自動車に搭載される二次電池またはキャパシタとして好適であるほか、AV機器、OA機器、通信機器などに用いられる二次電池、キャパシタとしても好適である。
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。実施例、比較例中の「部」および「%」は、特に断らない限り質量基準である。なお、実施例1~3および比較例1~5の蓄電デバイス用バインダー組成物は、正極を作製するための蓄電デバイス用バインダー組成物とし、実施例4、5の蓄電デバイス用バインダー組成物は、負極を作製するための蓄電デバイス用バインダー組成物とした。実施例6~10および比較例6~12の蓄電デバイス用バインダー組成物は、保護膜を形成するための蓄電デバイス用バインダー組成物とした。
7.1.1.蓄電デバイス用バインダー組成物の調製
電磁式撹拌機を備えた内容積約6Lのオートクレーブの内部を十分に窒素置換した後、脱酸素した純水2.5Lおよび乳化剤としてパーフルオロデカン酸アンモニウム25gを仕込み、350rpmで撹拌しながら60℃まで昇温した。次いで、単量体であるフッ化ビニリデン(VDF)70%および六フッ化プロピレン(HFP)30%からなる混合ガスを、内圧が20kg/cm2に達するまで仕込んだ。重合開始剤としてジイソプロピルパーオキシジカーボネートを20%含有するフロン113溶液25gを窒素ガスを使用して圧入し、重合を開始した。重合中は内圧が20kg/cm2に維持されるようVDF60.2%およびHFP39.8%からなる混合ガスを逐次圧入して、圧力を20kg/cm2に維持した。また、重合が進行するに従って重合速度が低下するため、3時間経過後に、先と同じ重合開始剤溶液の同量を窒素ガスを使用して圧入し、さらに3時間反応を継続した。反応液にメタクリル酸グリシジル(GMA)5部を添加し、3時間反応を継続した後、反応液を冷却すると同時に撹拌を停止し、未反応の単量体を放出した後に反応を停止することにより、重合体粒子を40%含有する水系分散体を得た。なお、得られた重合体粒子につき、19F-NMRおよび1H-NMRにより分析した結果、各単量体の質量組成比はVDF/HFP/GMA=40/5/5であった。
先ず、市販のリン酸鉄リチウム(LiFePO4)をめのう乳鉢で粉砕し、ふるいを用いて分級することにより、数平均粒子径(Db)が0.5μmである活物質粒子を得た。
曳糸性(%)=((TA-T0)/(TB-T0))×100 ・・・・・(3)
7.1.3.1.蓄電デバイス電極(正極)の製造
厚み30μmのアルミニウム箔からなる集電体の表面に、上記で調製した蓄電デバイス電極用スラリーを、乾燥後の膜厚が100μmとなるようにドクターブレード法によって均一に塗布し、120℃で20分間乾燥した。その後、膜(活物質層)の密度が表1に記載の値になるようにロールプレス機によりプレス加工することにより、蓄電デバイス電極(正極)を得た。
作製した蓄電デバイス電極を、幅2cm×長さ10cmの極板に切り出し、幅方向に直径2mmの丸棒に沿って電極板を折り曲げ回数100回にて繰り返し折り曲げ試験を行った。丸棒に沿った部分のクラックの大きさを目視により観察し計測し、クラック率を測定した。クラック率は、下記数式(4)によって定義した。
クラック率(%)={クラックの入った長さ(mm)÷極板全体の長さ(mm)}×100 ・・・・・(4)
二軸型プラネタリーミキサー(プライミクス株式会社製、商品名「TKハイビスミックス 2P-03」)に、ポリフッ化ビニリデン(PVDF)4部(固形分換算)、負極活物質としてグラファイト(昭和電工株式会社製、製品名「SCMG」、数平均粒子径=22μm)100部(固形分換算)、N-メチルピロリドン(NMP)80部を投入し、60rpmで1時間撹拌を行った。その後、さらにNMP20部を投入した後、撹拌脱泡機(株式会社シンキー製、製品名「あわとり練太郎」)を使用して、200rpmで2分間、次いで1,800rpmで5分間、さらに真空下において1,800rpmで1.5分間撹拌・混合することにより、対極(負極)用スラリーを調製した。
露点が-80℃以下となるようAr置換されたグローブボックス内で、上記で製造した対極(負極)を直径15.95mmに打ち抜き成型したものを、2極式コインセル(宝泉株式会社製、商品名「HSフラットセル」)上に載置した。次いで、直径24mmに打ち抜いたポリプロピレン製多孔膜からなるセパレータ(セルガード株式会社製、商品名「セルガード#2400」)を載置し、さらに、空気が入らないように電解液を500μL注入した後、上記で製造した正極を直径16.16mmに打ち抜き成型したものを載置し、前記2極式コインセルの外装ボディーをネジで閉めて封止することにより、リチウムイオン電池セル(蓄電デバイス)を組み立てた。なお、使用した電解液は、エチレンカーボネート/エチルメチルカーボネート=1/1(質量比)の溶媒に、LiPF6を1モル/Lの濃度で溶解した溶液である。
上記で製造した蓄電デバイスにつき、定電流(0.2C)にて充電を開始し、電圧が4.2Vになった時点で引き続き定電圧(4.2V)にて充電を続行し、電流値が0.01Cとなった時点を充電完了(カットオフ)として0.2Cでの充電容量を測定した。次いで、定電流(0.2C)にて放電を開始し、電圧が2.7Vになった時点を放電完了(カットオフ)とし0.2Cでの放電容量を測定した。
7.2.1.蓄電デバイス用バインダー組成物の調製
上記実施例1の「7.1.1.蓄電デバイス用バインダー組成物の調製」において、単量体の組成と乳化剤量を適宜に変更したほかは実施例1と同様にして、表1に示す組成の重合体粒子を含有する水系分散体を調製し、該水系分散体の固形分濃度に応じて水を減圧除去または追加することにより、固形分濃度40%の水系分散体を得た。得られた重合体粒子について数平均粒子径測定、長径と短径との比率算出結果、DSC測定を実施例1と同様にして行った。その結果を表1に併せて示した。
まず、上記実施例1の「7.1.2.蓄電デバイス電極用スラリーの調製」において、使用したふるいの目開きを適宜変更することにより、数平均粒子径(Db)が10μm、7μm、3μm、1μmである活物質粒子(LiFePO4)をそれぞれ調製した。このようにして得られた活物質粒子を以降の実施例及び比較例において使用した。なお、実施例2では10μm、比較例3では7μmの活物質粒子をそれぞれ使用し、表1に記載した種類および量の増粘剤を使用したほかは、実施例1における「7.1.2.蓄電デバイス電極用スラリーの調製」と同様にして電極(正極)用スラリーを調製し、その曳糸性を測定した。曳糸性の値を表1に併せて示した。
上記で得た各材料を使用したほかは、実施例1と同様にして蓄電デバイス電極(正極)および蓄電デバイスを製造し、評価した。その評価結果を表1に併せて示した。
7.3.1.蓄電デバイス用バインダー組成物の調製
上記実施例1の「7.1.1.蓄電デバイス用バインダー組成物の調製」において、単量体ガスの組成と乳化剤量を適宜に変更したほかは実施例1と同様にして、表1に示す組成の重合体粒子を含有する水系分散体を調製し、該水系分散体の固形分濃度に応じて水を減圧除去または追加することにより、固形分濃度40%の水系分散体を得た。得られた水系分散体へN-メチルピロリドン(NMP)を添加し、水を減圧除去することにより、NMPを液状媒体とする蓄電デバイス用バインダー組成物を得た。得られた重合体粒子について行った数平均粒子径測定、長径と短径との比率算出結果、DSC測定の結果を、表1に併せて示した。
実施例3では、上記で得られた数平均粒子径(Db)が3μmである活物質粒子(LiFePO4)を使用した。
上記の蓄電デバイス電極用スラリーを用いたほかは、実施例1における「7.1.3.蓄電デバイス電極および蓄電デバイスの製造ならびに評価」と同様にして蓄電デバイス電極(正極)および蓄電デバイスを製造し、評価した。評価結果は表1に併せて示した。
7.4.1.蓄電デバイス用バインダー組成物の調製
容量7Lのセパラブルフラスコの内部を十分に窒素置換した後、乳化剤「アデカリアソープSR1025」(商品名、株式会社ADEKA製)0.5部、スチレン(ST)25部、ブタジエン(BD)5部および水130部を順次仕込み、次いで油溶性重合開始剤であるアゾビスイソブチロニトリル0.5部を含有するテトラヒドロフラン溶液20mLを添加し、75℃に昇温して3時間反応を行い、さらに85℃で2時間反応を行った。反応液にメタクリル酸グリシジル(GMA)20部を添加し、3時間反応を継続した後、反応液を冷却すると同時に撹拌を停止し、重合体粒子を40%含有する水系分散体を得た。
上記で得られた数平均粒子径(Db)が7μmのリン酸鉄リチウム(LiFePO4)を活物質粒子として使用し、さらに表1に記載した種類および量の増粘剤を使用したほかは、実施例1における「7.1.2.蓄電デバイス電極用スラリーの調製」と同様にして電極(正極)用スラリーを調製し、その曳糸性を測定した。曳糸性の値を表1に併せて示した。
上記で得た各材料を使用したほかは、実施例1と同様にして蓄電デバイス電極(正極)および蓄電デバイスを製造し、評価した。その評価結果を表1に併せて示した。
7.5.1.蓄電デバイス用バインダー組成物の調製
上記比較例1の「7.4.1.蓄電デバイス用バインダー組成物の調製」において、単量体の組成と乳化剤量を適宜に変更したほかは比較例1と同様にして、表1に示す組成の重合体粒子を含有する水系分散体を調製し、該水系分散体の固形分濃度に応じて水を減圧除去または追加することにより、固形分濃度40%の水系分散体を得た。得られた重合体粒子について数平均粒子径測定、長径と短径との比率算出結果、DSC測定を実施例1と同様にして行った。その結果を表1に併せて示した。
比較例2では上記で得られた数平均粒子径(Db)が1μm、比較例4及び5では上記で得られた数平均粒子径(Db)が7μmのリン酸鉄リチウム(LiFePO4)を活物質粒子として使用し、さらに表1に記載した種類および量の増粘剤を使用したほかは、実施例1における「7.1.2.蓄電デバイス電極用スラリーの調製」と同様にして蓄電デバイス電極(正極)用スラリーを調製し、その曳糸性を測定した。曳糸性の値を表1に併せて示した。
上記で得た各材料を使用したほかは、実施例1と同様にして蓄電デバイス電極(正極)および蓄電デバイスを製造し、評価した。その評価結果を表1に併せて示した。
7.6.1.蓄電デバイス用バインダー組成物の調製
上記実施例1の「7.1.1.蓄電デバイス用バインダー組成物の調製」において、単量体の組成と乳化剤量を適宜に変更したほかは実施例1と同様にして、表1に示す組成の重合体粒子を含有する水系分散体を調製し、該水系分散体の固形分濃度に応じて水を減圧除去または追加することにより、固形分濃度40%の水系分散体を得た。得られた重合体粒子について数平均粒子径測定、長径と短径との比率算出結果、DSC測定を実施例1と同様にして行った。その結果を表1に併せて示した。
次いで、二軸型プラネタリーミキサー(プライミクス株式会社製、商品名「TKハイビスミックス 2P-03」)に増粘剤(商品名「CMC1150」、ダイセル化学工業株式会社製)7部(固形分換算)、負極活物質としてグラファイト(関東化学株式会社製、製品名「黒鉛末」をD50=10μmまで粉砕したもの)100部(固形分換算)、水68部を投入し、60rpmで1時間攪拌を行った。その後、上記で調製した蓄電デバイス用バインダー組成物2部(固形分換算)を加え、さらに1時間攪拌しペーストを得た。得られたペーストに水を投入し、固形分を50%に調製した後、攪拌脱泡機(株式会社シンキー製、商品名「泡とり練太郎」)を使用して、200rpmで2分間、1800rpmで5分間、さらに真空下において1800rpmで1.5分間攪拌混合することにより、蓄電デバイス電極用スラリーを調製した。実施例1における「7.1.2.蓄電デバイス電極用スラリーの調製」に記載した方法で負極用スラリーの曳糸性を測定した。その結果を表1に併せて示した。
7.6.3.1.蓄電デバイス電極(負極)の製造
厚み20μmの銅箔からなる集電体の表面に、上記で調製した蓄電デバイス電極(負極)用スラリーを、乾燥後の膜厚が150μmとなるようにドクターブレード法によって均一に塗布し、120℃で20分間乾燥した。その後、膜の密度が1.5g/cm3となるようにロールプレス機を使用してプレス加工することにより、蓄電デバイス電極(負極)を得た。
実施例1における「7.1.3.2.電極の評価(クラック率)」と同様にして、負極のクラック率を測定した。その結果を表1に併せて示した。
二軸型プラネタリーミキサー(プライミクス株式会社製、商品名「TKハイビスミックス 2P-03」)に電気化学デバイス電極用バインダー(株式会社クレハ製、商品名「KFポリマー#1120」)4.0部(固形分換算)、導電助剤(電気化学工業株式会社製、商品名「デンカブラック50%プレス品」)3.0部、正極活物質として粒径5μmのLiCoO2(ハヤシ化成株式会社製)100部(固形分換算)、N-メチルピロリドン(NMP)36部を投入し、60rpmで2時間攪拌を行った。得られたペーストにNMPを投入し、固形分を65%に調製した後、攪拌脱泡機(株式会社シンキー製、商品名「泡とり練太郎」)を使用して、200rpmで2分間、1800rpmで5分間、さらに真空下において1800rpmで1.5分間攪拌混合することにより、正極用スラリーを調製した。アルミ箔よりなる集電体の表面に、得られた正極用スラリーを、乾燥後の膜厚が80μmとなるようにドクターブレード法によって均一に塗布し、120℃で20分間乾燥処理した。その後、電極層の密度が3.0g/cm3となるようにロールプレス機によりプレス加工することにより、二次電池用正極を得た。
実施例1における「7.1.3.4.リチウムイオン電池セルの組立て」と同様にして、リチウムイオン電池セルを組み立てた。
実施例1における「7.1.3.5.蓄電デバイスの評価(放電レート特性の評価)」と同様にして、蓄電デバイスの評価を行った。その結果を表1に併せて示した。
7.7.1.蓄電デバイス用バインダー組成物の調製
上記実施例4の「7.6.1.蓄電デバイス用バインダー組成物の調製」において、単量体の組成と乳化剤量を適宜に変更し、グラファイトして昭和電工株式会社製の品名「SCMG」(Db=22μm)を用いたほかは実施例4と同様にして、表1に示す組成の重合体粒子を含有する水系分散体を調製し、該水系分散体の固形分濃度に応じて水を減圧除去または追加することにより、固形分濃度40%の水系分散体を得た。得られた重合体粒子について数平均粒子径測定、長径と短径との比率算出結果、DSC測定を実施例1と同様にして行った。その結果を表1に併せて示した。
表1に記載した種類および量の増粘剤を使用したほかは、実施例4における「7.6.2.蓄電デバイス電極(負極)用スラリーの調製」と同様にして蓄電デバイス電極(負極)用スラリーを調製し、その曳糸性を測定した。その結果を表1に併せて示した。
上記で得た各材料を使用したほかは、実施例4と同様にして蓄電デバイス電極(負極)および蓄電デバイスを製造し、評価した。その結果を表1に併せて示した。
<含フッ素化合物>
・VDF:フッ化ビニリデン
・HFP:六フッ化プロピレン
・TFE:四フッ化エチレン
<単官能(メタ)アクリル酸エステル>
・MMA:メタクリル酸メチル
・EHA:アクリル酸2-エチルヘキシル
<多官能(メタ)アクリル酸エステル>
・AMA:メタクリル酸アリル
・GMA:メタクリル酸グリシジル
・HEMA:メタクリル酸ヒドロキシエチル
<不飽和カルボン酸>
・AA:アクリル酸
・MAA:メタクリル酸
<他の単量体>
・AN:アクリロニトリル
・ST:スチレン
・BD:ブタジエン
<活物質>
・LFP:リン酸鉄リチウム(LiFePO4)
・GF:グラファイト
7.8.1.保護膜形成用スラリーの調製
無機粒子として酸化チタン(製品名「KR380」、チタン工業株式会社製、ルチル型、平均数粒子径0.38μm)を水100質量部に対して20質量部、上記実施例1の「7.1.1.蓄電デバイス用バインダー組成物の調製」で調製した蓄電デバイス用バインダー組成物を無機粒子に対して固形分換算で5質量部、増粘剤(ダイセル化学株式会社製、商品名「CMC1120」)1質量部を混合し、T.K.フィルミックス(R)56-50型(プライミクス株式会社製)を用いて混合分散処理を行い、酸化チタンが分散された保護膜形成用スラリーを調製した。
上記実施例1で作製した正極の正極活物質層の表面に、上記で得られた保護膜形成用スラリーをダイコート法を用いて塗布した後、120℃、5分間乾燥させることにより、正極活物質層表面に保護膜を形成した。なお、保護膜の厚みは3μmであった。
上記で製造したリチウムイオン電池セルを25℃の恒温槽に入れ、定電流(0.2C)にて充電を開始し、電圧が4.1Vになった時点で引き続き定電圧(4.1V)にて充電を続行し、電流値が0.01Cとなった時点を充電完了(カットオフ)とした。次いで、定電流(0.2C)にて放電を開始し、電圧が2.5Vになった時点を放電完了(カットオフ)とした(エージング充放電)。
残存容量率(%)=(C2/C1)×100 ・・・(5)
抵抗上昇率(%)=(EISb/EISa)×100 ・・・(6)
実施例2~5、比較例1~5で用いた蓄電デバイス用バインダー組成物を用いた以外は、実施例6と同様にして蓄電デバイスを製造し、評価した。評価結果は、表2に併せて示した。なお、実施例7~10の蓄電デバイス用バインダー組成物は、それぞれ実施例2~5の蓄電デバイス用バインダー組成物に対応しており、比較例6~10の蓄電デバイス用バインダー組成物は、それぞれ比較例1~5の蓄電デバイス用バインダー組成物に対応しているが、実施例7~10および比較例10では液状媒体の種類を表2に記載のものにそれぞれ変更した。
7.10.1.ポリイミドの合成
特開2009-87562号公報に記載の方法にてポリイミドを合成した。すなわち、冷却管と窒素ガス導入口が備えられた4つ口フラスコに、2,2-ビス(3,4-ジカルボキシフェニル)ヘキサフルオロプロパン二無水物1.0モルと、o-トリジンジイソシアネート0.95モルを固形分濃度が20質量%となるようにN-メチル-2-ピロリドン(NMP)と混合し、触媒としてジアザビシクロウンデセン0.01モルを加えて攪拌し、120℃で4時間反応させた。
上記実施例6の「7.8.1.保護膜形成用スラリーの調製」において、上記で得られたポリイミドのNMP溶液をバインダー溶液として用い、さらに水の代わりにNMPを用いた以外は実施例6と同様にして保護膜形成用スラリーを調製し、ポリイミドをバインダーとして用いた保護膜が形成された正極および蓄電デバイスを製造し、評価した。評価結果を表2に併せて示した。
7.11.1.ポリアミドイミドの合成
特開2007-154029号公報に記載の方法にてポリアミドイミドを合成した。すなわち、冷却管、窒素ガス導入管と攪拌機のついたフラスコにトリメリット酸無水物(TMA)0.7モル、3,3’、4,4’―ベンゾフェノンテトラカルボン酸無水物(BTDA)0.3モル、ナフタレンジイソシアネート(NDI)1モルとジアザビシクロウンデセン(DBU)0.01モルを固形分濃度が15%となるようにN-メチル-2-ピロリドン(NMP)と共に仕込み、80℃で約3時間反応させた。
上記実施例6の「7.8.1.保護膜形成用スラリーの調製」において、上記で得られたポリアミドイミドのNMP溶液をバインダー溶液として、また水の代わりにNMPを用いた以外は実施例6と同様にして保護膜形成用スラリーを調製し、ポリアミドイミドをバインダーとして用いた保護膜が形成された正極及び蓄電デバイスを製造し、評価した。評価結果を表2に併せて示した。
<無機粒子>
・酸化チタン:製品名「KR380」(チタン工業株式会社製、ルチル型、数平均粒子径0.38μm)をそのまま使用に供するか、または製品名「KR380」をめのう乳鉢で粉砕し、ふるいを用いて分級することにより、数平均粒子径が0.08μm、0.12μmである酸化チタンをそれぞれ調製して使用に供した。
・酸化アルミニウム:製品名「AKP‐3000」(住友化学株式会社製、数平均粒子径0.74μm)、または製品名「AKP‐50」(住友化学株式会社製、数平均粒子径0.22μm)を使用に供した。
・酸化ジルコニウム:製品名「UEP酸化ジルコニウム」(第一希元素化学工業株式会社製、数平均粒子径0.67μm)
・シリカ:製品名「シーホスター(R) KE-S50」(株式会社日本触媒製、数平均粒子径0.54μm)、または製品名「シーホスター(R) KE-S100」(株式会社日本触媒製、数平均粒子径0.98μm)を使用に供した。
・酸化マグネシウム:製品名「PUREMAG(R) FNM-G」(タテホ化学工業株式会社製、数平均粒子径0.50μm)
上記表1から明らかなように、実施例1~5に示した本発明に係る蓄電デバイス用バインダー組成物を用いて調製された蓄電デバイス電極用スラリーによれば、集電体と活物質層との間の結着性が良好となり、クラック率が低く、密着性に優れる蓄電デバイス電極を与えた。また、これらの蓄電デバイス電極を具備する蓄電デバイス(リチウムイオン二次電池)は、放電レート特性が良好であった。
Claims (16)
- 含フッ素化合物に由来する繰り返し単位(a)および多官能(メタ)アクリル酸エステルに由来する繰り返し単位(b)を含む重合体粒子(A)と、液状媒体(B)と、を含有する蓄電デバイス用バインダー組成物において、
前記重合体粒子(A)についてJIS K7121に準拠して示差走査熱量測定(DSC)を行ったときに、-30℃~30℃の温度範囲における吸熱ピークが一つおよび80℃~150℃の温度範囲における吸熱ピークが一つ観測されることを特徴とする、蓄電デバイス用バインダー組成物。 - 前記重合体粒子(A)中における、前記繰り返し単位(a)と前記繰り返し単位(b)との量比が質量基準で2:1~10:1の範囲にある、請求項1に記載の蓄電デバイス用バインダー組成物。
- 前記重合体粒子(A)の数平均粒子径が50~400nmの範囲にある、請求項1または請求項2に記載の蓄電デバイス用バインダー組成物。
- 前記重合体粒子(A)の長径(Rmax)と短径(Rmin)との比率(Rmax/Rmin)が1.1~1.5の範囲にある、請求項1ないし請求項3のいずれか一項に記載の蓄電デバイス用バインダー組成物。
- 前記重合体粒子(A)が、不飽和カルボン酸に由来する繰り返し単位(c)をさらに含み、
該重合体粒子(A)100質量部に対して、前記含フッ素化合物に由来する繰り返し単位(a)5~50質量部と、前記不飽和カルボン酸に由来する繰り返し単位(c)1~10質量部と、を含有する、請求項1ないし請求項4のいずれか一項に記載の蓄電デバイス用バインダー組成物。 - 蓄電デバイスの正極を作製するために用いられる、請求項1ないし請求項5のいずれか一項に記載の蓄電デバイス用バインダー組成物。
- 請求項1ないし請求項6のいずれか一項に記載の蓄電デバイス用バインダー組成物と、活物質と、を含有する蓄電デバイス電極用スラリー。
- 集電体と、前記集電体の表面に請求項7に記載の蓄電デバイス電極用スラリーを塗布、乾燥して作製された活物質層と、を備える蓄電デバイス電極。
- 請求項1ないし請求項5のいずれか一項に記載の蓄電デバイス用バインダー組成物と、無機粒子と、を含有する、保護膜形成用スラリー。
- 前記無機粒子が、シリカ、酸化チタン、酸化アルミニウム、酸化ジルコニウムおよび酸化マグネシウムよりなる群から選択される少なくとも1種の粒子である、請求項9に記載の保護膜形成用スラリー。
- 請求項9または請求項10に記載の保護膜形成用スラリーを用いて作製される保護膜。
- 請求項8に記載の蓄電デバイス電極を備える蓄電デバイス。
- 請求項11に記載の保護膜を備える蓄電デバイス。
- 正極と、負極と、をさらに備え、
前記保護膜が前記正極および前記負極の少なくとも一方の表面と接してなる、請求項13に記載の蓄電デバイス。 - 前記正極および前記負極の間に配置されたセパレータをさらに備える、請求項14に記載の蓄電デバイス。
- 正極と、負極と、前記正極および前記負極の間に配置されたセパレータと、をさらに備え、前記セパレータの表面が前記保護膜によって被覆された、請求項13に記載の蓄電デバイス。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280056131.0A CN103947020B (zh) | 2011-11-22 | 2012-11-12 | 蓄电设备用粘合剂组合物、蓄电设备电极用浆料、蓄电设备电极、保护膜形成用浆料、保护膜以及蓄电设备 |
KR1020147009514A KR20140106502A (ko) | 2011-11-22 | 2012-11-12 | 축전 디바이스용 결합제 조성물, 축전 디바이스 전극용 슬러리, 축전 디바이스 전극, 보호막 형성용 슬러리, 보호막, 및 축전 디바이스 |
JP2013509366A JP5348444B1 (ja) | 2011-11-22 | 2012-11-12 | 蓄電デバイス用バインダー組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極、保護膜形成用スラリー、保護膜、および蓄電デバイス |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-254749 | 2011-11-22 | ||
JP2011254749 | 2011-11-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013077212A1 true WO2013077212A1 (ja) | 2013-05-30 |
Family
ID=48469660
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/079271 WO2013077212A1 (ja) | 2011-11-22 | 2012-11-12 | 蓄電デバイス用バインダー組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極、保護膜形成用スラリー、保護膜、および蓄電デバイス |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5348444B1 (ja) |
KR (1) | KR20140106502A (ja) |
CN (1) | CN103947020B (ja) |
TW (1) | TWI540785B (ja) |
WO (1) | WO2013077212A1 (ja) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014123495A (ja) * | 2012-12-21 | 2014-07-03 | Denki Kagaku Kogyo Kk | 電極用バインダー組成物 |
JP2014209503A (ja) * | 2009-03-30 | 2014-11-06 | Jsr株式会社 | 電気化学デバイス電極バインダー用組成物 |
JP2014241197A (ja) * | 2013-06-11 | 2014-12-25 | Jsr株式会社 | 保護膜を作製するための組成物、保護膜およびその作製方法、ならびに蓄電デバイス |
WO2016002586A1 (ja) * | 2014-07-04 | 2016-01-07 | Jsr株式会社 | 蓄電デバイス用バインダー組成物 |
WO2016035286A1 (ja) * | 2014-09-05 | 2016-03-10 | 日本ゼオン株式会社 | 二次電池電極用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池 |
JP2016076493A (ja) * | 2013-06-20 | 2016-05-12 | Jsr株式会社 | 蓄電デバイス用組成物、蓄電デバイス用スラリー、蓄電デバイス電極およびその製造方法、保護膜およびその製造方法、ならびに蓄電デバイス |
CN105778834A (zh) * | 2016-03-21 | 2016-07-20 | 福建蓝海黑石科技有限公司 | 锂离子电池陶瓷隔膜用粘合剂及其制备方法 |
CN106206063A (zh) * | 2016-08-13 | 2016-12-07 | 代相臣 | 水系混合超级电容器及其制备方法 |
WO2017029902A1 (ja) * | 2015-08-14 | 2017-02-23 | 旭化成株式会社 | 電気化学素子用電極 |
JPWO2015008626A1 (ja) * | 2013-07-18 | 2017-03-02 | Jsr株式会社 | 蓄電デバイス用バインダー組成物、蓄電デバイス用スラリー、蓄電デバイス電極、セパレーターおよび蓄電デバイス |
JP2018536971A (ja) * | 2015-10-19 | 2018-12-13 | ソルベイ スペシャルティ ポリマーズ イタリー エス.ピー.エー. | コーティングされた電池セパレーター |
CN109713205A (zh) * | 2018-12-24 | 2019-05-03 | 福州大学 | 一种高安全性锂离子电池高温阻断隔膜的制备方法 |
JP2020126844A (ja) * | 2015-08-28 | 2020-08-20 | Jsr株式会社 | 蓄電デバイス用組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極、保護膜用スラリー、及び蓄電デバイス |
CN113764826A (zh) * | 2021-09-07 | 2021-12-07 | 广东九彩新材料有限公司 | 一种具有自粘性涂层的复合锂电隔膜及其制备方法 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104335394B (zh) * | 2012-09-11 | 2017-03-22 | Jsr株式会社 | 用于制作保护膜的组合物和保护膜以及蓄电器件 |
JP6601413B2 (ja) * | 2014-11-14 | 2019-11-06 | 日本ゼオン株式会社 | 二次電池電極用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池 |
JP6764468B2 (ja) | 2015-08-25 | 2020-09-30 | エルジー・ケム・リミテッド | 接着層を含む電気化学素子用の複合分離膜及びこれを備えた電気化学素子 |
CN109314243B (zh) * | 2016-07-12 | 2022-08-05 | 日本瑞翁株式会社 | 固体电解质电池用粘结剂组合物 |
JP6579383B2 (ja) * | 2016-08-10 | 2019-09-25 | 荒川化学工業株式会社 | リチウムイオン二次電池用セパレータ、リチウムイオン二次電池用セパレータの製造方法、及びリチウムイオン二次電池 |
PL3506394T3 (pl) * | 2016-08-25 | 2024-03-04 | Zeon Corporation | Kompozycja dla warstw funkcjonalnych niewodnej baterii akumulatorowej, warstwa funkcjonalna dla niewodnych baterii akumulatorowych, niewodna bateria akumulatorowa i sposób wytwarzania elektrody dla niewodnych baterii akumulatorowych |
TWI770351B (zh) * | 2018-02-09 | 2022-07-11 | 日商昭和電工股份有限公司 | 非水系電池電極用漿料,以及非水系電池電極及非水系電池之製造方法 |
CN109786749B (zh) * | 2019-02-18 | 2021-03-30 | 珠海冠宇电池股份有限公司 | 一种交联sbr微球粘结剂及制备方法及含有该粘结剂的锂离子电池 |
US20220302455A1 (en) * | 2019-08-13 | 2022-09-22 | Eneos Materials Corporation | Composition for electricity storage devices, slurry for electricity storage device electrodes, electricity storage device electrode, and electricity storage device |
CN115312777A (zh) * | 2022-09-07 | 2022-11-08 | 湖北亿纬动力有限公司 | 一种低曲折度厚电极及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10302797A (ja) * | 1997-04-21 | 1998-11-13 | Jsr Corp | 電池電極バインダー |
JP2003317722A (ja) * | 2002-04-26 | 2003-11-07 | Kureha Chem Ind Co Ltd | 非水系二次電池電極用バインダー組成物、電極合剤組成物、電極および二次電池 |
JP2006185887A (ja) * | 2004-11-30 | 2006-07-13 | Matsushita Electric Ind Co Ltd | 非水電解液二次電池 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200740913A (en) * | 2006-02-02 | 2007-11-01 | Jsr Corp | Polymer composition, paste for secondary battery electrode, and secondary battery electrode |
JP5177040B2 (ja) * | 2008-03-31 | 2013-04-03 | Jsr株式会社 | キャパシタ電極バインダー用組成物、キャパシタ電極用スラリーおよびキャパシタ電極 |
JP5262323B2 (ja) * | 2008-06-11 | 2013-08-14 | ソニー株式会社 | 多孔性保護膜付き負極、及び多孔性保護膜付き負極の製造方法 |
-
2012
- 2012-11-12 CN CN201280056131.0A patent/CN103947020B/zh active Active
- 2012-11-12 JP JP2013509366A patent/JP5348444B1/ja active Active
- 2012-11-12 KR KR1020147009514A patent/KR20140106502A/ko not_active Application Discontinuation
- 2012-11-12 WO PCT/JP2012/079271 patent/WO2013077212A1/ja active Application Filing
- 2012-11-21 TW TW101143480A patent/TWI540785B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10302797A (ja) * | 1997-04-21 | 1998-11-13 | Jsr Corp | 電池電極バインダー |
JP2003317722A (ja) * | 2002-04-26 | 2003-11-07 | Kureha Chem Ind Co Ltd | 非水系二次電池電極用バインダー組成物、電極合剤組成物、電極および二次電池 |
JP2006185887A (ja) * | 2004-11-30 | 2006-07-13 | Matsushita Electric Ind Co Ltd | 非水電解液二次電池 |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014209503A (ja) * | 2009-03-30 | 2014-11-06 | Jsr株式会社 | 電気化学デバイス電極バインダー用組成物 |
JP2014123495A (ja) * | 2012-12-21 | 2014-07-03 | Denki Kagaku Kogyo Kk | 電極用バインダー組成物 |
JP2014241197A (ja) * | 2013-06-11 | 2014-12-25 | Jsr株式会社 | 保護膜を作製するための組成物、保護膜およびその作製方法、ならびに蓄電デバイス |
JP2016076493A (ja) * | 2013-06-20 | 2016-05-12 | Jsr株式会社 | 蓄電デバイス用組成物、蓄電デバイス用スラリー、蓄電デバイス電極およびその製造方法、保護膜およびその製造方法、ならびに蓄電デバイス |
JPWO2015008626A1 (ja) * | 2013-07-18 | 2017-03-02 | Jsr株式会社 | 蓄電デバイス用バインダー組成物、蓄電デバイス用スラリー、蓄電デバイス電極、セパレーターおよび蓄電デバイス |
JP5904350B1 (ja) * | 2014-07-04 | 2016-04-13 | Jsr株式会社 | 蓄電デバイス用バインダー組成物 |
WO2016002586A1 (ja) * | 2014-07-04 | 2016-01-07 | Jsr株式会社 | 蓄電デバイス用バインダー組成物 |
US10505195B2 (en) | 2014-07-04 | 2019-12-10 | Jsr Corporation | Method for producing electrical storage device electrode with binder composition |
US10290873B2 (en) | 2014-09-05 | 2019-05-14 | Zeon Corporation | Binder composition for secondary battery electrode, slurry composition for secondary battery electrode, electrode for secondary battery, and secondary battery |
KR102418499B1 (ko) | 2014-09-05 | 2022-07-06 | 니폰 제온 가부시키가이샤 | 이차 전지 전극용 바인더 조성물, 이차 전지 전극용 슬러리 조성물, 이차 전지용 전극 및 이차 전지 |
WO2016035286A1 (ja) * | 2014-09-05 | 2016-03-10 | 日本ゼオン株式会社 | 二次電池電極用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池 |
KR20170053615A (ko) * | 2014-09-05 | 2017-05-16 | 니폰 제온 가부시키가이샤 | 이차 전지 전극용 바인더 조성물, 이차 전지 전극용 슬러리 조성물, 이차 전지용 전극 및 이차 전지 |
JPWO2016035286A1 (ja) * | 2014-09-05 | 2017-06-15 | 日本ゼオン株式会社 | 二次電池電極用バインダー組成物、二次電池電極用スラリー組成物、二次電池用電極および二次電池 |
WO2017029902A1 (ja) * | 2015-08-14 | 2017-02-23 | 旭化成株式会社 | 電気化学素子用電極 |
JP2020126844A (ja) * | 2015-08-28 | 2020-08-20 | Jsr株式会社 | 蓄電デバイス用組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極、保護膜用スラリー、及び蓄電デバイス |
JP2018536971A (ja) * | 2015-10-19 | 2018-12-13 | ソルベイ スペシャルティ ポリマーズ イタリー エス.ピー.エー. | コーティングされた電池セパレーター |
CN105778834A (zh) * | 2016-03-21 | 2016-07-20 | 福建蓝海黑石科技有限公司 | 锂离子电池陶瓷隔膜用粘合剂及其制备方法 |
CN106206063A (zh) * | 2016-08-13 | 2016-12-07 | 代相臣 | 水系混合超级电容器及其制备方法 |
CN109713205A (zh) * | 2018-12-24 | 2019-05-03 | 福州大学 | 一种高安全性锂离子电池高温阻断隔膜的制备方法 |
CN109713205B (zh) * | 2018-12-24 | 2020-07-31 | 福州大学 | 一种高安全性锂离子电池高温阻断隔膜的制备方法 |
CN113764826A (zh) * | 2021-09-07 | 2021-12-07 | 广东九彩新材料有限公司 | 一种具有自粘性涂层的复合锂电隔膜及其制备方法 |
CN113764826B (zh) * | 2021-09-07 | 2022-08-23 | 广东九彩新材料有限公司 | 一种具有自粘性涂层的复合锂电隔膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN103947020B (zh) | 2016-04-06 |
CN103947020A (zh) | 2014-07-23 |
JP5348444B1 (ja) | 2013-11-20 |
KR20140106502A (ko) | 2014-09-03 |
JPWO2013077212A1 (ja) | 2015-04-27 |
TW201334273A (zh) | 2013-08-16 |
TWI540785B (zh) | 2016-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5348444B1 (ja) | 蓄電デバイス用バインダー組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極、保護膜形成用スラリー、保護膜、および蓄電デバイス | |
JP5673984B2 (ja) | 保護膜及びそれを作製するための組成物、スラリー、並びに蓄電デバイス | |
JP5488857B1 (ja) | 保護膜を作製するための組成物および保護膜、ならびに蓄電デバイス | |
TWI431842B (zh) | 電極用接合劑組成物,電極用漿料,電極及蓄電裝置 | |
TWI390791B (zh) | 正電極用黏合劑組成物 | |
JP5652633B1 (ja) | リチウムイオン二次電池用組成物、リチウムイオン二次電池用スラリー、リチウムイオン二次電池用電極、リチウムイオン二次電池用セパレーターおよびリチウムイオン二次電池 | |
US20160079007A1 (en) | Binder composition for power storage devices | |
KR101433512B1 (ko) | 전극용 결합제 조성물, 전극용 슬러리, 전극 및 축전 디바이스 | |
JP2013098123A (ja) | 電極用バインダー組成物、電極用スラリー、電極、および蓄電デバイス | |
JP5459526B1 (ja) | 蓄電デバイス用バインダー組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極、保護膜形成用スラリー、保護膜、および蓄電デバイス | |
JP2013084502A (ja) | 電極用バインダー組成物 | |
JP2015153638A (ja) | 保護層の形成方法および蓄電デバイス | |
JP5601476B2 (ja) | 電極用バインダー組成物 | |
JP6083525B2 (ja) | 保護膜を作製するための組成物、保護膜およびその作製方法、ならびに蓄電デバイス |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201280056131.0 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2013509366 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12851536 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20147009514 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12851536 Country of ref document: EP Kind code of ref document: A1 |