WO2009147765A1 - 電池用組成物 - Google Patents
電池用組成物 Download PDFInfo
- Publication number
- WO2009147765A1 WO2009147765A1 PCT/JP2008/073303 JP2008073303W WO2009147765A1 WO 2009147765 A1 WO2009147765 A1 WO 2009147765A1 JP 2008073303 W JP2008073303 W JP 2008073303W WO 2009147765 A1 WO2009147765 A1 WO 2009147765A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- basic functional
- functional group
- carbon
- derivative
- solvent
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 228
- 125000000524 functional group Chemical group 0.000 claims abstract description 210
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 182
- 239000006185 dispersion Substances 0.000 claims abstract description 180
- 239000002270 dispersing agent Substances 0.000 claims abstract description 173
- 239000002904 solvent Substances 0.000 claims abstract description 136
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 77
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000011230 binding agent Substances 0.000 claims abstract description 62
- 239000007774 positive electrode material Substances 0.000 claims abstract description 55
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical class C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 150000003918 triazines Chemical class 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 45
- 239000002482 conductive additive Substances 0.000 claims abstract description 40
- 239000007773 negative electrode material Substances 0.000 claims abstract description 35
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 58
- 238000011282 treatment Methods 0.000 claims description 49
- 238000004519 manufacturing process Methods 0.000 claims description 41
- 239000012752 auxiliary agent Substances 0.000 claims description 34
- 239000003586 protic polar solvent Substances 0.000 claims description 24
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Chemical class CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 23
- 150000004056 anthraquinones Chemical class 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 16
- 230000004931 aggregating effect Effects 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000010 aprotic solvent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 168
- 229910052799 carbon Inorganic materials 0.000 description 144
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 127
- 239000000975 dye Substances 0.000 description 73
- 125000001424 substituent group Chemical group 0.000 description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 49
- 238000011156 evaluation Methods 0.000 description 43
- 230000000694 effects Effects 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 40
- 239000006229 carbon black Substances 0.000 description 33
- 239000002033 PVDF binder Substances 0.000 description 30
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 29
- 229920006369 KF polymer Polymers 0.000 description 28
- 229910052751 metal Inorganic materials 0.000 description 26
- 239000002184 metal Substances 0.000 description 26
- 239000011164 primary particle Substances 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- -1 lithium transition metal Chemical class 0.000 description 24
- 230000002829 reductive effect Effects 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 22
- 239000011149 active material Substances 0.000 description 20
- 239000002585 base Substances 0.000 description 20
- 239000000370 acceptor Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000011324 bead Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000002798 polar solvent Substances 0.000 description 17
- 238000007599 discharging Methods 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000006230 acetylene black Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 239000003973 paint Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 10
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 239000004917 carbon fiber Substances 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 230000006872 improvement Effects 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000002931 mesocarbon microbead Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 8
- 239000002134 carbon nanofiber Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 239000008213 purified water Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- GDALETGZDYOOGB-UHFFFAOYSA-N Acridone Natural products C1=C(O)C=C2N(C)C3=CC=CC=C3C(=O)C2=C1O GDALETGZDYOOGB-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 125000004450 alkenylene group Chemical group 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000003282 alkyl amino group Chemical group 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 125000000732 arylene group Chemical group 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 125000005017 substituted alkenyl group Chemical group 0.000 description 6
- 125000000547 substituted alkyl group Chemical group 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000006232 furnace black Substances 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 229960004063 propylene glycol Drugs 0.000 description 5
- 235000013772 propylene glycol Nutrition 0.000 description 5
- 125000003107 substituted aryl group Chemical group 0.000 description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- 229940093475 2-ethoxyethanol Drugs 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 229940093915 gynecological organic acid Drugs 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 4
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 4
- 239000003273 ketjen black Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000434 metal complex dye Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-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 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 241001561902 Chaetodon citrinellus Species 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229940052303 ethers for general anesthesia Drugs 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 229920001197 polyacetylene Polymers 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- 230000002123 temporal effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- ZWPUOFSQNASCII-UHFFFAOYSA-N 1-(2-ethoxyethoxy)butane Chemical compound CCCCOCCOCC ZWPUOFSQNASCII-UHFFFAOYSA-N 0.000 description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 241000984084 Helianthemum nummularium subsp. grandiflorum Species 0.000 description 2
- 101000713585 Homo sapiens Tubulin beta-4A chain Proteins 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 102100036788 Tubulin beta-4A chain Human genes 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000001000 anthraquinone dye Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- IPBFYZQJXZJBFQ-UHFFFAOYSA-N gamma-octalactone Chemical compound CCCCC1CCC(=O)O1 IPBFYZQJXZJBFQ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-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
- 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
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 2
- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical class C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 150000003012 phosphoric acid amides Chemical class 0.000 description 2
- 239000001007 phthalocyanine dye Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- JTQQDDNCCLCMER-CLFAGFIQSA-N (z)-n-[(z)-octadec-9-enyl]octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCNCCCCCCCC\C=C/CCCCCCCC JTQQDDNCCLCMER-CLFAGFIQSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-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
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- PGRNEGLBSNLPNP-UHFFFAOYSA-N 1,6-dichloro-3-methylhex-1-ene Chemical compound ClC=CC(C)CCCCl PGRNEGLBSNLPNP-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- YKSVXVKIYYQWBB-UHFFFAOYSA-N 1-butylpiperazine Chemical compound CCCCN1CCNCC1 YKSVXVKIYYQWBB-UHFFFAOYSA-N 0.000 description 1
- PVMCQBPJKPMOKM-UHFFFAOYSA-N 1-cyclopentylpiperazine Chemical compound C1CCCC1N1CCNCC1 PVMCQBPJKPMOKM-UHFFFAOYSA-N 0.000 description 1
- FXHRAKUEZPSMLJ-UHFFFAOYSA-N 1-methyl-1,4-diazepane Chemical compound CN1CCCNCC1 FXHRAKUEZPSMLJ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QOZOFODNIBQPGN-UHFFFAOYSA-N 2,4-dimethylpiperidine Chemical compound CC1CCNC(C)C1 QOZOFODNIBQPGN-UHFFFAOYSA-N 0.000 description 1
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- VOXJHLBQCSZQDM-UHFFFAOYSA-N 2-(4-aminoanilino)-6-[3-(dibutylamino)propylamino]-1h-1,3,5-triazin-4-one Chemical compound CCCCN(CCCC)CCCNC1=NC(O)=NC(NC=2C=CC(N)=CC=2)=N1 VOXJHLBQCSZQDM-UHFFFAOYSA-N 0.000 description 1
- BTEYOILJVIONOI-UHFFFAOYSA-N 2-(4-methylpiperidin-1-yl)ethanamine Chemical compound CC1CCN(CCN)CC1 BTEYOILJVIONOI-UHFFFAOYSA-N 0.000 description 1
- NNWUEBIEOFQMSS-UHFFFAOYSA-N 2-Methylpiperidine Chemical compound CC1CCCCN1 NNWUEBIEOFQMSS-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- CJNRGSHEMCMUOE-UHFFFAOYSA-N 2-piperidin-1-ylethanamine Chemical compound NCCN1CCCCC1 CJNRGSHEMCMUOE-UHFFFAOYSA-N 0.000 description 1
- PTHDBHDZSMGHKF-UHFFFAOYSA-N 2-piperidin-2-ylethanol Chemical compound OCCC1CCCCN1 PTHDBHDZSMGHKF-UHFFFAOYSA-N 0.000 description 1
- IDWRJRPUIXRFRX-UHFFFAOYSA-N 3,5-dimethylpiperidine Chemical compound CC1CNCC(C)C1 IDWRJRPUIXRFRX-UHFFFAOYSA-N 0.000 description 1
- SPVVMXMTSODFPU-UHFFFAOYSA-N 3-methyl-n-(3-methylbutyl)butan-1-amine Chemical compound CC(C)CCNCCC(C)C SPVVMXMTSODFPU-UHFFFAOYSA-N 0.000 description 1
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 description 1
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 description 1
- JMUCXULQKPWSTJ-UHFFFAOYSA-N 3-piperidin-1-ylpropan-1-amine Chemical compound NCCCN1CCCCC1 JMUCXULQKPWSTJ-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical compound CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BNVJFVRHKCXSKB-UHFFFAOYSA-N C(CC)NN(NCCC)CCCC Chemical compound C(CC)NN(NCCC)CCCC BNVJFVRHKCXSKB-UHFFFAOYSA-N 0.000 description 1
- ZLCHQENPCWGQMX-UHFFFAOYSA-N C(CCC)NN(NCCCC)CC Chemical compound C(CCC)NN(NCCCC)CC ZLCHQENPCWGQMX-UHFFFAOYSA-N 0.000 description 1
- ZTUKETFIANAUMH-UHFFFAOYSA-N C(CCC)NN(NCCCC)CCCC Chemical compound C(CCC)NN(NCCCC)CCCC ZTUKETFIANAUMH-UHFFFAOYSA-N 0.000 description 1
- DHSRTDUQGNBAAJ-UHFFFAOYSA-N C(CCCCCCCC=C/CCCCCCCC)NN(NCCCCCCCCC=C/CCCCCCCC)CC Chemical compound C(CCCCCCCC=C/CCCCCCCC)NN(NCCCCCCCCC=C/CCCCCCCC)CC DHSRTDUQGNBAAJ-UHFFFAOYSA-N 0.000 description 1
- OWBIYFCJOZKVQJ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)NN(NCCCCCCCCCCCCCCCCCC)CC Chemical compound C(CCCCCCCCCCCCCCCCC)NN(NCCCCCCCCCCCCCCCCCC)CC OWBIYFCJOZKVQJ-UHFFFAOYSA-N 0.000 description 1
- RMTHCFYCIDEQSH-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)NN(NCCCCCCCCCCCCCCCCCC)CCCC Chemical compound C(CCCCCCCCCCCCCCCCC)NN(NCCCCCCCCCCCCCCCCCC)CCCC RMTHCFYCIDEQSH-UHFFFAOYSA-N 0.000 description 1
- BYRDXIBAOYIIRN-UHFFFAOYSA-N C1(CCCC1)N1CCNCC1.NN1CCN(CC1)C Chemical compound C1(CCCC1)N1CCNCC1.NN1CCN(CC1)C BYRDXIBAOYIIRN-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
- XMCPMYFHKPRRTQ-UHFFFAOYSA-N CCCCCCN(NCC)NCC Chemical compound CCCCCCN(NCC)NCC XMCPMYFHKPRRTQ-UHFFFAOYSA-N 0.000 description 1
- QTDYLWCJIPXWCU-UHFFFAOYSA-N CCCCCN(NC)NC Chemical compound CCCCCN(NC)NC QTDYLWCJIPXWCU-UHFFFAOYSA-N 0.000 description 1
- DPNFBBYMACYVIB-UHFFFAOYSA-N CCCCCN(NCC)NCC Chemical compound CCCCCN(NCC)NCC DPNFBBYMACYVIB-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 241000557626 Corvus corax Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HXEACLLIILLPRG-YFKPBYRVSA-N L-pipecolic acid Chemical compound [O-]C(=O)[C@@H]1CCCC[NH2+]1 HXEACLLIILLPRG-YFKPBYRVSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910015015 LiAsF 6 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
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 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
- 229940043279 diisopropylamine Drugs 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N ethylene glycol dimethyl ether Natural products COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- SRJOCJYGOFTFLH-UHFFFAOYSA-N isonipecotic acid Chemical compound OC(=O)C1CCNCC1 SRJOCJYGOFTFLH-UHFFFAOYSA-N 0.000 description 1
- HXEACLLIILLPRG-RXMQYKEDSA-N l-pipecolic acid Natural products OC(=O)[C@H]1CCCCN1 HXEACLLIILLPRG-RXMQYKEDSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LLOCHSZLPLWNJG-UHFFFAOYSA-N n',n'-bis(2-methylpropyl)pentane-1,5-diamine Chemical compound CC(C)CN(CC(C)C)CCCCCN LLOCHSZLPLWNJG-UHFFFAOYSA-N 0.000 description 1
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- GCOWZPRIMFGIDQ-UHFFFAOYSA-N n',n'-dimethylbutane-1,4-diamine Chemical compound CN(C)CCCCN GCOWZPRIMFGIDQ-UHFFFAOYSA-N 0.000 description 1
- OYRMAWDRAFHHJK-UHFFFAOYSA-N n'-dodecyl-n-methylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCNCCCNC OYRMAWDRAFHHJK-UHFFFAOYSA-N 0.000 description 1
- QKYWADPCTHTJHQ-UHFFFAOYSA-N n,2-dimethylpropan-1-amine Chemical compound CNCC(C)C QKYWADPCTHTJHQ-UHFFFAOYSA-N 0.000 description 1
- HFOVYSKOTZHZRV-UHFFFAOYSA-N n,n-bis(ethylamino)butan-1-amine Chemical compound CCCCN(NCC)NCC HFOVYSKOTZHZRV-UHFFFAOYSA-N 0.000 description 1
- YPLIFKZBNCNJJN-UHFFFAOYSA-N n,n-bis(ethylamino)ethanamine Chemical compound CCNN(CC)NCC YPLIFKZBNCNJJN-UHFFFAOYSA-N 0.000 description 1
- NYIODHFKZFKMSU-UHFFFAOYSA-N n,n-bis(methylamino)ethanamine Chemical compound CCN(NC)NC NYIODHFKZFKMSU-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- DVFVBAPHBZWJFX-UHFFFAOYSA-N n-(2-methylpropyl)butan-2-amine Chemical compound CCC(C)NCC(C)C DVFVBAPHBZWJFX-UHFFFAOYSA-N 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- RWIVICVCHVMHMU-UHFFFAOYSA-N n-aminoethylmorpholine Chemical compound NCCN1CCOCC1 RWIVICVCHVMHMU-UHFFFAOYSA-N 0.000 description 1
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 1
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 description 1
- XQOIBQBPAXOVGP-UHFFFAOYSA-N n-ethyl-2-methylpropan-2-amine Chemical compound CCNC(C)(C)C XQOIBQBPAXOVGP-UHFFFAOYSA-N 0.000 description 1
- FQBQBRBAJDVVOH-UHFFFAOYSA-N n-ethyl-3-methylbutan-2-amine Chemical compound CCNC(C)C(C)C FQBQBRBAJDVVOH-UHFFFAOYSA-N 0.000 description 1
- BTCXINMWPKVQNR-UHFFFAOYSA-N n-ethyl-n'-hexylethane-1,2-diamine Chemical compound CCCCCCNCCNCC BTCXINMWPKVQNR-UHFFFAOYSA-N 0.000 description 1
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- XJINZNWPEQMMBV-UHFFFAOYSA-N n-methylhexan-1-amine Chemical compound CCCCCCNC XJINZNWPEQMMBV-UHFFFAOYSA-N 0.000 description 1
- SZEGKVHRCLBFKJ-UHFFFAOYSA-N n-methyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNC SZEGKVHRCLBFKJ-UHFFFAOYSA-N 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- QYNZYUUXSVZDJO-UHFFFAOYSA-N n-propylbutan-2-amine Chemical compound CCCNC(C)CC QYNZYUUXSVZDJO-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- VUNPWIPIOOMCPT-UHFFFAOYSA-N piperidin-3-ylmethanol Chemical compound OCC1CCCNC1 VUNPWIPIOOMCPT-UHFFFAOYSA-N 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- JHHZLHWJQPUNKB-UHFFFAOYSA-N pyrrolidin-3-ol Chemical compound OC1CCNC1 JHHZLHWJQPUNKB-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000011029 spinel Chemical group 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- YKSGNOMLAIJTLT-UHFFFAOYSA-N violanthrone Chemical compound C12=C3C4=CC=C2C2=CC=CC=C2C(=O)C1=CC=C3C1=CC=C2C(=O)C3=CC=CC=C3C3=CC=C4C1=C32 YKSGNOMLAIJTLT-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- 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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a composition used for producing an electrode constituting a battery and a method for producing the composition.
- the electrode composition of the present invention is suitably used for the production of a lithium secondary battery.
- the present invention provides a lithium secondary comprising an electrode having excellent discharge characteristics or charge characteristics at a large current, cycle characteristics, and conductivity of the electrode mixture, and having low contact resistance between the electrode current collector and the electrode mixture. It relates to batteries.
- lithium secondary batteries are being actively developed.
- a positive electrode in which an electrode mixture composed of a positive electrode active material containing lithium ions, a conductive additive, an organic binder, and the like is fixed to the surface of a current collector of metal foil, and lithium ion desorption.
- a negative electrode is used in which an electrode mixture made of an insertable negative electrode active material, a conductive additive and an organic binder is fixed to the surface of a metal foil current collector.
- lithium transition metal composite oxides such as lithium cobaltate and lithium manganate are used as the positive electrode active material, but these have low electronic conductivity and have sufficient battery performance when used alone. I can't get it. Therefore, attempts have been made to improve the conductivity by reducing the internal resistance of the electrode by adding a carbon material such as carbon black (for example, acetylene black) as a conductive additive. In particular, reducing the internal resistance of the electrode is very important in enabling discharge with a large current and improving charge and discharge efficiency.
- carbon black for example, acetylene black
- graphite graphite
- graphite is usually used as the negative electrode active material.
- carbon black such as acetylene black
- charge and discharge characteristics are improved by adding carbon black such as acetylene black as a conductive aid together with graphite. This is because the graphite particles that are generally used are large, so if graphite alone is used, the gap when filled in the electrode layer will increase.
- carbon black is used as a conductive additive, fine carbon black is used. It seems that the contact area increases by filling the gaps between the graphite particles and the resistance decreases.
- the conductive effect is reduced if the dispersion of the conductive aid is insufficient. In this way, reducing the internal resistance of the electrode is one of the very important factors in enabling discharge with a large current and improving the charge / discharge efficiency.
- Patent Document 1 and Patent Document 2 attempt a method of forming a coating film in which a conductive agent such as carbon black is dispersed on the collector electrode as an electrode underlayer. If it is bad, sufficient effect cannot be obtained.
- Patent Documents 3 and 4 describe examples in which a surfactant is used as a dispersant when carbon black is dispersed in a solvent.
- the surfactant since the surfactant has a weak adsorption force on the surface of the carbon material, it is necessary to increase the amount of the surfactant added in order to obtain good dispersion stability. As a result, the amount of the active material that can be contained Decreases and the battery capacity decreases. Further, if the surfactant is not sufficiently adsorbed on the carbon material, the carbon material will aggregate. Further, a general surfactant has a remarkably low dispersion effect in an organic solvent as compared with dispersion in an aqueous solution.
- Patent Document 5 and Patent Document 6 when dispersing carbon black in a solvent, the dispersion state of the carbon slurry is improved by adding a dispersion resin, and the carbon slurry and the active material are mixed.
- a method for producing an electrode mixture is disclosed.
- this method improves the dispersibility of carbon black, a large amount of dispersed resin is required to disperse fine carbon black having a large specific surface area, and a dispersed resin having a large molecular weight is carbon black. Since the surface is covered, the conductive network is obstructed and the resistance of the electrode is increased. As a result, the effect of improving the dispersion of carbon black may be offset.
- an important factor for improving the efficiency of charging / discharging is the improvement of the wettability of the electrode with respect to the electrolytic solution. Since the electrode reaction occurs at the contact interface between the electrode material surface and the electrolytic solution, it is important that the electrolytic solution penetrates into the electrode and the electrode material is well wetted.
- a method of promoting the electrode reaction a method of increasing the surface area of the electrode by using a fine active material or a conductive auxiliary agent has been studied. There is a problem that it is difficult to improve battery performance because the contact area of the battery does not increase.
- Patent Document 7 discloses a method in which fine voids are provided between active material particles by including carbon fibers having a fiber diameter of 1 to 1000 nm in the electrode. .
- carbon fibers are usually intertwined in a complicated manner, uniform dispersion is difficult, and a uniform electrode cannot be produced simply by mixing carbon fibers.
- carbon fiber is directly oxidized, the conductivity and strength of carbon fiber are reduced. There is a problem of end up.
- Patent Document 8 discloses a method for improving the wettability by adsorbing a surfactant such as a higher fatty acid alkali salt to a negative electrode material mainly composed of carbon powder.
- a surfactant such as a higher fatty acid alkali salt
- the agent often does not have sufficient dispersion performance in a non-aqueous system, and a uniform electrode coating film cannot be obtained. In these examples, the total performance including the dispersibility of the electrode material was insufficient.
- lithium secondary batteries also have problems related to safety such as battery performance deterioration due to reduction / deposition of metal components on the negative electrode, and excessive heat generation and ignition due to occurrence of a short circuit.
- causes of performance degradation and short-circuiting due to metal components include (1) metal impurities such as copper and iron in the manufacturing process, and (2) metal ions contained in the positive electrode, current collector, battery container, etc. in the electrolyte. It is conceivable that, after elution, the metal ions are reduced and deposited on the negative electrode, and (3) metal ions are eluted from the positive electrode active material due to the deterioration of the positive electrode, and are reduced and deposited on the negative electrode.
- Patent Document 9 suppresses the precipitation at the negative electrode by trapping the cation eluted from the positive electrode on the separator surface by introducing a cation exchange group on the surface of the separator. Attempts have been made. However, in this case, to obtain a separator in which a cation exchange group is introduced on the surface by immersing a nonwoven fabric as a separator substrate in an aqueous solution of acrylic acid (monomer) and a polymerization initiator and irradiating ultraviolet rays in a nitrogen atmosphere. The manufacturing process becomes complicated and is not suitable for mass production. In this case, ions that have passed through the separator cannot be captured.
- the present invention provides a battery composition containing a conductive auxiliary agent, which achieves dispersion stabilization without inhibiting the conductivity of the conductive auxiliary agent, and electrolysis of the conductive auxiliary agent that is a carbon material. It aims at improving the battery performance of the battery produced using this by improving the wettability with respect to a liquid, and providing the function which capture
- JP 2000-123823 A Japanese Patent Laid-Open No. 2002-298753 JP-A-63-236258 JP-A-8-190912 Japanese Patent Laid-Open No. 2003-157846 JP-T 2006-51695 JP 2005-063955 A JP-A-6-60877 Japanese Patent Laid-Open No. 2002-25527
- the present inventors have an organic dye derivative having a basic functional group and a basic functional group when the carbon material as a conductive additive is dispersed in a solvent.
- a dispersion of carbon material particles having excellent dispersion stability can be prepared by adding one or more selected from an anthraquinone derivative, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group as a dispersant. Furthermore, it has been found that the wettability of the carbon material particles to the battery electrolyte is improved.
- the battery is considered to be caused by lowering the resistance of the electrode and improving the adhesion between the electrode current collector and the electrode mixture or the active material and the conductive additive.
- the present inventors have found a performance improvement effect, a wettability improvement effect with respect to an electrolytic solution, and a metal ion precipitation suppression effect, and have made the present invention.
- the battery composition of the present invention can be used for a lithium secondary battery, a nickel hydride secondary battery, a nickel cadmium secondary battery, an alkaline manganese battery, a lead battery, a fuel cell, a capacitor, etc., and in particular, a lithium secondary battery. It is suitable for use in.
- the present invention provides at least one selected from organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, or triazine derivatives having basic functional groups.
- the present invention relates to a battery composition comprising a dispersant and a carbon material as a conductive additive.
- the present invention also relates to the battery composition described above, further comprising a solvent.
- the present invention further relates to the above battery composition, further comprising an acid having a molecular weight of 300 or less.
- the present invention also relates to the above battery composition, wherein the acid is a volatile acid.
- the present invention relates to the above battery composition, wherein the dispersed particle diameter (D 50 ) of the carbon material as a conductive additive is 2 ⁇ m or less.
- the present invention further relates to the above battery composition, further comprising a binder component.
- the present invention also relates to the above battery composition, wherein the binder component is a polymer compound containing a fluorine atom in the molecule.
- the present invention also relates to the above battery composition, wherein the solvent has a relative dielectric constant of 15 or more and 200 or less.
- the present invention also relates to the above battery composition, wherein the battery composition comprises a solvent having an acceptor number of 15 or more and 60 or less.
- the present invention includes a solvent having a solubility parameter hydrogen bond component (SP value ( ⁇ h)) of 5 (cal / cm 3 ) 1/2 or more and 20 (cal / cm 3 ) 1/2 or less. It relates to the battery composition as described above. Moreover, this invention relates to said battery composition characterized by including a protic solvent. The present invention also relates to the battery composition described above, wherein the battery composition is a combination of a protic solvent and an aprotic solvent. The present invention further relates to the above battery composition, further comprising a positive electrode active material or a negative electrode active material.
- SP value ( ⁇ h) solubility parameter hydrogen bond component
- the present invention provides at least one selected from organic dye derivatives having a basic functional group, anthraquinone derivatives having a basic functional group, acridone derivatives having a basic functional group, or triazine derivatives having a basic functional group.
- the present invention relates to a method for producing a battery composition, wherein at least a carbon material as a conductive additive is dispersed in a solvent in the presence of a dispersant.
- the present invention provides at least one selected from organic dye derivatives having a basic functional group, anthraquinone derivatives having a basic functional group, acridone derivatives having a basic functional group, or triazine derivatives having a basic functional group.
- a method for producing a battery composition comprising mixing a positive electrode active material, a negative electrode active material, or a binder component in a dispersion obtained by dispersing a carbon material as a conductive additive in a solvent in the presence of a dispersant. About.
- the present invention provides at least one selected from organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, or triazine derivatives having basic functional groups.
- the present invention relates to a method for producing a battery composition characterized by co-dispersing a carbon material as a conductive additive and a positive electrode active material, a negative electrode active material, or a binder component in a solvent in the presence of a dispersant.
- the present invention further relates to a method for producing the above battery composition, wherein the dispersion is carried out in the presence of an acid having a molecular weight of 300 or less.
- the present invention also relates to a method for producing a battery composition in which the protic solvent is distilled off from the above-mentioned composition using both a protic solvent and an aprotic solvent by heating and / or decompression.
- the present invention provides at least one selected from organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, or triazine derivatives having basic functional groups.
- organic dye derivatives having basic functional groups an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a basic functional group
- the present invention relates to a method for producing a battery composition as described above, wherein a carbon material is used as a conductive additive that has been pretreated with one or more dispersants selected from triazine derivatives.
- the present invention provides a carbon material as a conductive aid pretreated with a dispersant, an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, Alternatively, the present invention relates to a method for producing the above battery composition, which is a carbon material that has been dry-treated in the presence of one or more dispersants selected from triazine derivatives having a basic functional group.
- the present invention provides a carbon material as a conductive aid pretreated with a dispersant, an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, Or it is related with the manufacturing method of said battery composition characterized by the carbon material processed in the liquid phase in presence of 1 or more types of dispersing agents chosen from the triazine derivative which has a basic functional group.
- the present invention provides a carbon material as a conductive aid pretreated with a dispersant, an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, Alternatively, one or more dispersants selected from triazine derivatives having a basic functional group and a carbon material are mixed or dispersed in a liquid phase while the dispersant acts on the surface of the carbon material, and the dispersant acts. It is related with the manufacturing method of said battery composition characterized by being a carbon material obtained through the process of aggregating a carbon material.
- the present invention is characterized in that the step of removing foreign matter is performed during the step of causing the dispersant to act on the surface of the carbon material and / or before the step of aggregating the carbon material on which the dispersant has acted.
- the present invention relates to a method for producing a battery composition.
- the present invention also relates to the above-described method for producing a battery composition, wherein the treatment in the liquid phase is an organic solvent treatment.
- the present invention also relates to the above-described method for producing a battery composition, wherein the treatment in the liquid phase is an aqueous treatment.
- the present invention is a lithium secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium
- the present invention relates to a lithium secondary battery, wherein the positive electrode mixture layer or the negative electrode mixture layer is formed using the battery composition including a positive electrode active material or a negative electrode active material.
- the present invention is a lithium secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium, An electrode underlayer is formed between the positive electrode mixture layer and the current collector or between the negative electrode mixture layer and the current collector using any one of the battery compositions described above.
- the present invention relates to a lithium secondary battery.
- the present invention relates to a lithium secondary battery in which an electrode mixture layer and / or an electrode underlayer is formed using the battery composition produced by the above production method.
- the dispersion stability of the conductive assistant is excellent, and the dispersion stability is achieved without hindering the conductivity of the conductive assistant, and
- the wettability with respect to the electrolytic solution is improved and the precipitation of metal ions is suppressed. Therefore, by using the battery composition according to a preferred embodiment of the present invention, for example, lithium Battery performance of secondary batteries and the like can be improved comprehensively.
- the battery composition in the present invention is selected from an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group. Although it contains the carbon material as a dispersing aid of a seed
- a carbon material is most preferable.
- the carbon material is not particularly limited as long as it is a conductive carbon material, but graphite, carbon black, carbon nanotube, carbon nanofiber, carbon fiber, fullerene, etc. alone or in combination of two or more. Can be used. From the viewpoint of conductivity, availability, and cost, it is preferable to use carbon black.
- Carbon black is a furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially ketjen black using ethylene heavy oil as a raw material.
- Ordinarily oxidized carbon black, hollow carbon and the like can also be used.
- the oxidation treatment of carbon is performed by treating carbon at a high temperature in the air or by secondary treatment with nitric acid, nitrogen dioxide, ozone, etc., for example, such as phenol group, quinone group, carboxyl group, carbonyl group.
- This is a treatment for directly introducing (covalently bonding) an oxygen-containing polar functional group to the carbon surface, and is generally performed to improve the dispersibility of carbon.
- it since it is common for the conductivity of carbon to fall, so that the introduction amount of a functional group increases, it is preferable to use the carbon which has not been oxidized.
- the specific surface area (BET) determined from the adsorption amount of nitrogen is 20 m 2 / g or more and 1500 m 2 / g or less, preferably 50 m 2 / g or more and 1500 m 2 / g or less, more preferably 100 m 2. / G or more and 1500 m 2 / g or less are desirable.
- BET specific surface area
- the particle size of the carbon black to be used is preferably 0.005 to 1 ⁇ m, particularly preferably 0.01 to 0.2 ⁇ m in terms of primary particle size.
- the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.
- Examples of commercially available carbon black include Toka Black # 4300, # 4400, # 4500, # 5500 (Tokai Carbon Co., Furnace Black), Printex L, etc. (Degussa, Furnace Black), Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULTRA, etc., Conductex SC ULTRA, Conductex 975 ULTRA, etc., PUER BLACK100, 115, 205, etc. (Columbian, Furnace Black), # 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3030B, # 3030B # 3350B, # 3400B, # 5400B, etc.
- the dispersant in the present invention is selected from the group consisting of organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups. It is what In particular, the use of a triazine derivative represented by the following general formula (1) or an organic dye derivative represented by the general formula (6) is preferable.
- X 1 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or -X 2 -Y-X 3 - represents,
- X 2 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - represents, X 3 each independently -NH- or, -O Y represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which is composed of 1 to 20 carbon atoms.
- P represents a substituent represented by any one of the general formulas (2), (3) and the general formula (4).
- Q is —O—R 2 , —NH—R 2 , a halogen group, —X 1 —R 1, or a substituent represented by any one of the general formulas (2), (3), or (4) Represents.
- R 2 represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
- X 4 is a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 - or, -X 5 -Y-X 6 - represents a.
- X 5 is -NH- or represents -O-, X 6 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 - or -CH 2 - Represents.
- Y represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent.
- v represents an integer of 1 to 10.
- R 3 and R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or R 3 and R 4.
- a hydrogen atom is preferable because it is considered that the effect of suppressing metal deposition in the battery is high.
- R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.
- R 9 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
- n represents an integer of 1 to 4.
- R 1 represents an organic dye residue, a heterocyclic residue that may have a substituent, an aromatic ring residue that may have a substituent, or a group represented by the following general formula (5).
- T represents —X 8 —R 10 or W 1
- U represents —X 9 —R 11 or W 2
- W 1 and W 2 are each independently —O—R 2 , —NH—R 2 , a halogen group, or a substituent represented by any one of the general formulas (2), (3), or (4) Represents.
- R 2 represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
- X 7 represents an -NH- or -O-
- X 8 and X 9 are each independently -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH- or -CH 2 NHCOCH 2 NH—
- Y represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, having 1 to 20 carbon atoms.
- R 10 and R 11 each independently represents an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic ring residue which may have a substituent.
- Examples of the organic dye residue represented by R 1 in the general formula (1) and R 10 and R 11 in the general formula (5) include azo dyes such as diketopyrrolopyrrole dyes, azo, disazo, and polyazo.
- Anthraquinone dyes such as phthalocyanine dyes, diaminodianthraquinones, anthrapyrimidines, flavantrons, anthanthrones, indantrons, pyrantrons, violanthrones, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes And dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complex dyes, and the like.
- an organic dye residue that is not a metal complex dye.
- Examples of the heterocyclic residue and aromatic ring residue represented by R 1 in the general formula (1) and R 10 and R 11 in the general formula (5) include thiophene, furan, pyridine, pyrazine, triazine, Examples include pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, and acridone.
- heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro groups.
- hydroxyl group alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.)
- a substituent such as a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be.
- Y in the general formula (1) and the general formula (5) represents an alkylene group, an alkenylene group or an arylene group which may have a substituent having 20 or less carbon atoms, but may preferably be substituted. Examples include a phenylene group, a biphenylene group, a naphthylene group, or an alkylene group that may have a side chain having 10 or less carbon atoms.
- General formula (6)
- Z is at least one selected from the group represented by the following general formula (7), (8) or general formula (9).
- n represents an integer of 1 to 4.
- X 4 is a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 - or, -X 5 -Y-X 6 - represents a.
- X 5 is -NH- or represents -O-
- X 6 represents a direct bond, -SO 2 -, - CO - , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 - or -CH 2 -
- Y represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent.
- v represents an integer of 1 to 10.
- R 3 and R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R 3 and R 4. Represents an optionally substituted heterocyclic residue containing additional nitrogen, oxygen or sulfur atoms.
- a hydrogen atom is preferable because it is considered that the effect of suppressing metal deposition in the battery is high.
- R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.
- R 9 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
- R 12 represents an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic ring residue which may have a substituent. Examples of the organic dye residue represented by R 12 include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrones, indans.
- Anthraquinone dyes such as throne, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes
- examples thereof include dyes and metal complex dyes.
- an organic dye residue that is not a metal complex dye.
- heterocyclic residue and aromatic ring residue represented by R 12 examples include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benzine.
- examples include triazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, acridone and the like.
- heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro groups.
- hydroxyl group alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.)
- a substituent such as a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be.
- Examples of the amine component used for forming the substituents represented by the general formulas (2) to (4) and the general formulas (6) to (8) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropyl Amine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2- Ethylhexyl) amine, dioctylua ,
- the method for synthesizing the organic dye derivative, anthraquinone derivative and acridone derivative having a basic functional group and the triazine derivative having a basic functional group according to the present invention is not particularly limited, but JP-A-54-62227. JP, 56-118462, JP 56-166266, JP 60-88185, JP 63-305173, JP 3-2676, JP 11-11 It can be synthesized by the method described in 199796.
- substituents represented by the formulas (10) to (13) into an organic dye, anthraquinone or acridone
- these substituents and amine components for example, N, N-dimethylaminopropylamine, N-methyl
- amine components for example, N, N-dimethylaminopropylamine, N-methyl
- an organic dye having a carboxyl group, anthraquinone, or acridone is synthesized by a known method, and then thionyl chloride or the like in an aromatic solvent such as benzene. And the like, and the like.
- the substituent represented by the formula (10) is a sulfonic acid group
- the substituent represented by the formula (11) is a carboxylic acid group.
- a metal or a salt of the above amine may be formed.
- organic dye is an azo dye
- a substituent represented by formula (7) to formula (9) or the following general formula (14) is introduced in advance into the diazo component or coupling component, and then coupled.
- An azo organic dye derivative can also be produced by carrying out the reaction.
- X 1 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or -X 2 -Y-X 3 - represents,
- X 2 is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO- or -NHSO 2 - represents,
- X 3 each independently -NH- or -O- Y represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which is composed of 1 to 20 carbon atoms.
- P represents a substituent represented by any one of the general formulas (2), (3) and the general formula (4).
- Q is —O—R 2 , —NH—R 2 , a halogen group, —X 1 —R 1, or a substituent represented by any one of the general formulas (2), (3), or (4) Represents.
- R 2 represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
- the triazine derivative having a basic functional group of the present invention is represented by, for example, cyanuric chloride as a starting material, and at least one chlorine of cyanuric chloride represented by formula (7) to formula (9) or general formula (14). It is obtained by reacting an amine component (for example, N, N-dimethylaminopropylamine or N-methylpiperazine etc.) that forms a substituent, and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols. It is done.
- an amine component for example, N, N-dimethylaminopropylamine or N-methylpiperazine etc.
- the above-mentioned dispersant is considered to exert a dispersing effect when the added dispersant acts on the surface of the carbon material (for example, adsorption).
- An organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group is completely or partially dissolved in a solvent, and the solution It is considered that the action (for example, adsorption) of these dispersants on the carbon material proceeds by adding and mixing the carbon material therein.
- the wetting of the carbon surface with respect to the solvent is promoted by the polarity of the basic functional group of the dispersant acting (for example, adsorbing) on the surface of the carbon material, and the aggregation of the carbon material is likely to be solved.
- the dispersion stability of a conductive support agent can be further increased by using together with the acid as a dispersion support agent mentioned later.
- an acid as a dispersion aid in order to obtain good dispersion and dispersion stability of the carbon material.
- the acid used at this time is not particularly limited, but hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, inorganic compounds such as salts obtained by the reaction of strong acid and weak base, organic acids such as carboxylic acids, phosphoric acids and sulfonic acids are used. it can. Among them, it is preferable to use an acid that decomposes or volatilizes in the drying process at the time of electrode preparation, and it is preferable to use an acid having a molecular weight of 300 or less, preferably 200 or less.
- an acid having low reactivity with the electrode active material described later it is preferable to use an acid having low reactivity with the electrode active material described later, and organic acids, particularly carboxylic acids are particularly preferable.
- organic acids particularly carboxylic acids are particularly preferable.
- These acids act with the basic functional groups of organic dye derivatives with basic functional groups, anthraquinone derivatives with basic functional groups, acridone derivatives with basic functional groups, or triazine derivatives with basic functional groups (for example, by forming ion pairs by neutralization (salt formation) and by polarization or dissociation of ion pairs (salts), the solubility of these dispersants increases and these dispersants act (for example, adsorb). Electrical interaction (for example, electrostatic repulsion between dispersant cations adsorbed on the carbon material surface, repulsion effect by the electric double layer formed by dissociated acid anions, etc.) is induced on the carbon material surface, carbon It seems that deagglomeration of the material is promoted.
- the addition of these acids is also expected to suppress deterioration due to the dehydrofluorination reaction of the binder by acidification of the system when a polyvinylidene fluoride binder described later is used.
- a good dispersion From these, good dispersion can be obtained without degrading the conductivity of the carbon material. Then, by using the battery composition of the present invention in which the carbon material is well dispersed, an electrode in which the carbon material is uniformly dispersed can be produced.
- the dispersant having a polar functional group is present on the surface of the carbon material, the wettability of the carbon material with respect to the electrolytic solution is improved, and the above-described uniform dispersion effect is achieved. This improves the wettability of the electrode with respect to the electrolyte.
- Each of the dispersants of the present invention has a good dispersion effect and wettability improvement effect, but captures metal ions in the electrolyte solution with basic functional groups and suppresses battery performance degradation and short circuit due to metal deposition. It is preferable because the effect is great.
- solvent used in the present invention examples include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, and phosphoric acid.
- examples include esters, ethers, nitriles, water and the like.
- a polar solvent having a relative dielectric constant of 15 or more and 200 or less, preferably 15 or more and 100 or less, and more preferably 20 or more and 100 or less can provide good dispersion stability of the carbon material.
- the relative dielectric constant of the solvent is less than 15, sufficient dispersion may not be obtained, and even if a solvent having a relative dielectric constant exceeding 100 is used, a significant dispersion improvement effect may not be obtained.
- the relative dielectric constant is one of the indices indicating the strength of the polarity of the solvent, and is described in Asahara et al., “Solvent Handbook” (Kodansha Scientific Co., Ltd., 1990).
- Examples of the solvent having a relative dielectric constant of 15 or more include methyl alcohol (relative dielectric constant: 33.1), ethyl alcohol (23.8), 2-propanol (18.3), 1-butanol (17.1). 1,2-ethanediol (38.66), 1,2-propanediol (32.0), 1,3-propanediol (35.0), 1,4-butanediol (31.1), diethylene glycol (31.69), 2-methoxyethanol (16.93), 2-ethoxyethanol (29.6), 2-aminoethanol (37.7), acetone (20.7), methyl ethyl ketone (18.51), Formamide (111.0), N-methylformamide (182.4), N, N-dimethylformamide (36.71), N-methylacetamide (191.3) N, N-dimethylacetamide (37.78), N-methylpropionamide (172.2), N-methylpyrrolidone (32.0), hexamethylphosphoric triamide (29.6), dimethyl
- the dispersion stability of the carbon material was found to be influenced by the electron acceptability of the solvent. It is preferable to include a solvent having a large electron-accepting effect. Particularly, a solvent having an acceptor number of 15 or more is preferable, but a solvent having 25 to 60 is more preferable.
- the number of acceptors is 31 P-NMR chemical shift of SbCl 5 .Et 3 PO. As a standard, the chemical shift in dichloroethane is 100, and the chemical shift in hexane is 0. Dimensionless number given by relative chemical shift.
- the number of acceptors is a scale for measuring the strength of electron acceptability of various solvents, and the larger the value, the stronger the electron acceptability of the solvent. For the number of acceptors, see V.A. Gutman (translated by Otsuki, Okada), “Donor and Acceptor” (Japan Society for the Science of Publishing Co., Ltd. 1983). Depending on the relative dielectric constant of the solvent, if a solvent having an acceptor number of less than 15 is used, a sufficient dispersion stabilizing effect may not be obtained.
- Examples of the solvent having an acceptor number of 15 or more include N, N-dimethylformamide (16.0), benzonitrile (15.5), acetonitrile (18.9), dimethyl sulfoxide (19.3), nitromethane (20 .5), chloroform (23.1), 2-propanol (33.5), ethanol (37.9), methanol (41.5), water (54.8) and the like, but are not limited thereto. .
- the dispersion stability of the carbon material tended to be influenced by the hydrogen bonding properties of the solvent. It is preferable to include a solvent having a large hydrogen bonding property, and a solvent having a solubility parameter hydrogen bonding component (SP value ( ⁇ h)) of 5 (cal / cm 3 ) 1/2 or more is preferable, but 8 (cal / cm 3 ) A solvent of 1/2 or more and 20 (cal / cm 3 ) 1/2 or less is more preferable.
- SP value ( ⁇ h) solubility parameter hydrogen bonding component
- the solubility parameter is a value defined as the square root of the cohesive energy density of the liquid.
- the London dispersion force component the force between dipoles
- the idea of dividing into three components, the component and the hydrogen bond component is C.I. M.M. Hansen, K .; Skaarup: J.M. Paint Tech. 39 [511] (1967).
- the SP value ( ⁇ h) is a parameter for the hydrogen bonding component, and the larger the value, the greater the hydrogen bonding action of the solvent.
- the solvent having a solubility parameter hydrogen bonding component (SP value ( ⁇ h)) of 5 (cal / cm 3 ) 1/2 or more include, for example, aniline (5.0), 2- (2-butoxyethoxy) ethane ( 5.2), diacetone alcohol (5.3), N, N-dimethylformamide (5.5), 1-pentanol (6.8), 2-ethoxyethanol (7.0), 1-butanol ( 7.7), 1-propyl alcohol (8.5), ethanol (9.5), diethylene glycol (9.7), ethanolamine (10.4), methanol (10.9), 1,2-propanediol (11.4), 1,2-ethanediol (12.7), water (16.7) and the like, but are not limited thereto.
- the solvent to be used preferably contains a protic polar solvent.
- a protic polar solvent is a proton-donating solvent, which has the ability to release protons in the solvent itself, and is considered to be highly effective in stabilizing anionic species by solvation.
- Preferable protic polar solvents include, for example, alcohols and glycols having a hydroxyl group, and amide solvents in which nitrogen is monoalkylated, such as N-methylformamide, N-methylacetamide, and N-methylpropionamide. , And water, but are not limited thereto.
- a polar solvent having a large acceptor number, a polar solvent having a hydrogen bonding component (SP value ( ⁇ h)) having a solubility parameter, and a protic polar solvent have a strong solvating power with respect to a dispersant having a basic functional group. It contributes to the dispersion of the carbon material by improving the solubility of the dispersant and the wettability of the carbon material on which the dispersant acts (for example, adsorbing), and promoting the polarization of the basic functional group of the dispersant.
- the basic functional group (Lewis base) of the dispersant has a high electron density, it is considered that a solvent having a high polarity (a large dielectric constant) and a strong electron accepting property or hydrogen bonding property is likely to act.
- a polar solvent having a large acceptor number A polar solvent having a large hydrogen bonding component (SP value ( ⁇ h)) and a protic polar solvent having a solubility parameter are desirable because they are considered to have a high effect of stabilizing the ion pair or its anion species by solvation. Furthermore, a solvent having a particularly high relative dielectric constant is preferable because it seems to promote dissociation of ion pairs.
- a solvent having a large acceptor number a solvent having a hydrogen bonding component (SP value ( ⁇ h)) having a solubility parameter
- a protic solvent a relative dielectric constant
- SP value ( ⁇ h) a hydrogen bonding component having a solubility parameter
- an aprotic polar solvent is a polar solvent that does not have the ability to release protons and does not self-dissociate.
- Aprotic polar solvents do not cause self-association due to hydrogen bonding, and the solvent itself aggregates. The nature is weak. Therefore, the penetrating power of the carbon material into the aggregate is strong, and an effect of helping the dispersing agent to act on the surface of the carbon material is expected.
- the aprotic polar solvent is weak in cohesiveness of the solvent itself and has a strong dissolving power and can dissolve various dispersants and resins, it is excellent in versatility.
- Preferred aprotic polar solvents include, for example, amide solvents obtained by dialkylating nitrogen such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide and N, N-diethylacetamide.
- amide solvents obtained by dialkylating nitrogen such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide and N, N-diethylacetamide.
- N-methylpyrrolidone, hexamethylphosphoric triamide, dimethyl sulfoxide and the like but are not limited thereto.
- the solvent in the present invention one kind selected from an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group
- the carbon material as the conductive aid, the acid as the dispersion aid, and the solvent an electrode active material or a binder component, which will be described later, is added to the dispersibility of the carbon material described above.
- an electrode active material or a binder component which will be described later, is added to the dispersibility of the carbon material described above.
- it reacts considering the reactivity with an electrode active material, the solubility with respect to a binder component, etc. It is preferable to select a solvent having a high dispersion effect, low reactivity with the active material, and high solubility of the binder component.
- a protic polar solvent and an aprotic polar solvent in order to satisfy the effect of promoting the dispersion stability of the carbon material, the reactivity with the electrode active material, and the solubility of the binder component, it is preferable to use a protic polar solvent and an aprotic polar solvent in combination, In particular, it is preferable to use a protic polar solvent having a large number of acceptors or a hydrogen bonding component (SP value ( ⁇ h)) having a solubility parameter and an aprotic polar solvent in combination.
- the ratio of protic polar solvent / aprotic polar solvent is preferably 1/99 to 60/40.
- the solubility of the binder When the ratio is less than 1/99, sufficient dispersion stability of the carbon material may not be obtained, and when it exceeds 60/40, the solubility of the binder may be reduced. However, even if the solubility of the binder decreases as a result of excessive use of the protic solvent to improve the dispersibility of the carbon material as a conductive additive, the protic solvent is retained by heating, decompression, etc. after dispersion. By leaving, the solubility of the binder can be improved.
- composition of the present invention is used for a positive electrode mixture or a negative electrode mixture, at least a positive electrode active material or a negative electrode active material is contained in addition to the dispersant, the carbon material as a conductive additive, and a solvent.
- Metal compounds such as a metal oxide which can dope or intercalate lithium ion, a metal sulfide, a conductive polymer, etc. can be used.
- metal oxides such as Fe, Co, Ni, and Mn
- composite oxides with lithium and inorganic compounds such as transition metal sulfides.
- transition metal oxide powders such as MnO, V 2 O 5 , V 6 O 13 , TiO 2 , layered structure lithium nickelate, lithium cobaltate, lithium manganate, spinel structure lithium manganate, etc.
- lithium and transition metals examples thereof include composite oxide powders of lithium and transition metals, lithium iron phosphate materials that are phosphate compounds having an olivine structure, and transition metal sulfide powders such as TiS 2 and FeS.
- conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used.
- the negative electrode active material lithium ion doping or capable of intercalating Li metal or its alloy, tin alloy, silicon alloy negative electrode, Li X Fe 2 O 3, Li X Fe 3 O 4 Metal oxides such as Li X WO 2 , conductive polymers such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, Alternatively, carbonaceous powders such as natural graphite, carbon black, mesophase carbon black, resin-fired carbon materials, gas-grown carbon fibers, carbon fibers, and the like are used.
- the composition of the present invention preferably further contains a binder component.
- binders to be used ethylene, propylene, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylonitrile, styrene, vinyl butyral, vinyl acetal, vinyl pyrrolidone, etc.
- cellulose resins such as: rubbers such as styrene-butadiene rubber and fluororubber; conductive resins such as polyaniline and polyacetylene.
- the modified body and mixture of these resin, and a copolymer may be sufficient.
- a high molecular compound containing a fluorine atom in the molecule for example, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene, etc. from the viewpoint of resistance.
- the weight average molecular weight of these resins as a binder is preferably 10,000 to 1,000,000.
- the resistance of the binder may decrease.
- the resistance of the binder is improved, but the viscosity of the binder itself is increased and the workability is lowered.
- composition of the present invention can be used for a positive electrode mixture or a negative electrode mixture.
- the ratio of the active material to the total solid content in the electrode mixture paste is preferably 80% by weight or more and 98.5% by weight or less.
- an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine having a basic functional group in the total solid content in the electrode mixture paste The ratio of the solid content of one or more dispersants selected from the derivatives and the carbon material as the conductive assistant is preferably 0.5% by weight or more and 19% by weight or less.
- the proportion of the binder component in the total solid content in the electrode mixture paste is preferably 1% by weight or more and 10% by weight or less.
- the proper viscosity of the electrode mixture paste depends on the method of applying the electrode mixture paste, but generally it is preferably 100 mPa ⁇ s or more and 30,000 mPa ⁇ s or less.
- the positive / negative electrode composite paste in the present invention not only has excellent dispersibility of the carbon material particles as a conductive additive, but also has an effect of alleviating aggregation of the positive / negative electrode active material. Because the carbon material particles, which are conductive assistants, have excellent dispersibility, the energy of mixing and dispersing the carbon material as the conductive assistant and the positive and negative electrode active materials in the solvent is the aggregate of the carbon material (conductive assistant). It is believed that the active material can be efficiently transferred to the active material without being obstructed, and as a result, the dispersibility of the positive and negative electrode active materials can be improved.
- the carbon material particles which are conductive assistants, can be uniformly coordinated and adhered around the positive electrode active material, and excellent conductivity and adhesion can be imparted to the positive electrode mixture layer. Further, since the conductivity is improved, the amount of the carbon material added as a conductive auxiliary agent can be reduced, so that the amount of the positive electrode active material added can be relatively increased, and the capacity which is a large characteristic of the battery can be increased. Can be bigger.
- the positive electrode mixture paste of the present invention has very little aggregation of the positive electrode active material and the carbon material (conducting aid), a uniform coating film having high smoothness can be obtained when applied to a current collector. The adhesion between the current collector and the positive electrode mixture is improved.
- the dispersant having a basic functional group acts (for example, adsorbs) on the surface of the carbon material (conducting aid), the surface of the positive electrode active material such as a lithium transition metal composite oxide and the carbon material (conducting aid). Agent) The interaction with the surface is strengthened, and the adhesion between the positive electrode active material and the carbon material (conductive aid) is improved as compared with the case where a dispersant having a basic functional group is not used.
- the negative electrode mixture paste when a carbon material-based active material is used as the negative electrode active material, an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, a base added as a dispersant
- the aggregation of the carbon material-based active material is alleviated by the effect of the acridone derivative having a functional functional group or the triazine derivative having a basic functional group.
- the carbon material particles (conductive aid) can be uniformly coordinated and adhered around the negative electrode active material, and excellent conductivity and adhesion can be imparted to the negative electrode mixture layer.
- composition of the present invention can also be used for an electrode underlayer.
- an organic dye derivative having a basic functional group an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group
- a dispersion comprising the above dispersant, a carbon material as a conductive aid, an acid as a dispersion aid, and a solvent may be used as it is, but the binder component is added and used as an electrode base paste. It is preferable.
- the ratio of the carbon material as a conductive additive to the total solid content of the composition used for the electrode underlayer is preferably 5% by weight or more and 95% by weight or less, more preferably 10% by weight or more and 90% by weight or less. If the carbon material as the conductive auxiliary agent is small, the conductivity of the underlayer may not be maintained. On the other hand, if the carbon material as the conductive auxiliary agent is excessive, the resistance of the coating film may be reduced.
- the appropriate viscosity of the electrode base paste depends on the method of applying the electrode base paste, but generally it is preferably 100 mPa ⁇ s or more and 30,000 mPa ⁇ s or less.
- the composition of the present invention is selected from, for example, an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group.
- the production method includes at least one dispersion selected from an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group.
- Disperse the agent in the solvent by dissolving or completely dissolving the agent in the solvent, and adding and mixing the carbon material as a conductive aid in the solution, while allowing these dispersants to act on the carbon material (for example, adsorption).
- the concentration of the carbon material in the dispersion at this time is preferably 1% by weight or more and 50% by weight or less, although it depends on the characteristic values of the carbon material such as the specific surface area and surface functional group amount of the carbon material used.
- the concentration of the carbon material is too low, the production efficiency is deteriorated.
- the concentration of the carbon material is too high, the viscosity of the dispersion is remarkably increased, and the dispersion efficiency and the handling property of the dispersion may be lowered.
- the amount of one or more dispersants selected from organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, or triazine derivatives having basic functional groups is as follows:
- the specific surface area of the carbon material as the conductive additive used is determined.
- the dispersant is 0.5 to 40 parts by weight, preferably 1 to 35 parts by weight, more preferably 2 to 30 parts by weight with respect to 100 parts by weight of the carbon material. Or less. If the amount of the dispersant is small, a sufficient dispersion effect cannot be obtained, and even if added in excess, a significant dispersion improvement effect cannot be obtained.
- an organic dye derivative having a basic functional group an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a basic functional group
- an acid it is preferable to add an acid as a dispersion aid.
- the basic dye contained in an organic dye derivative having a basic functional group an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group It is preferable to add 0.1 to 30 equivalents relative to the functional group amount, and more preferably 1 to 20 equivalents.
- a disperser usually used for pigment dispersion or the like can be used as a device for dispersing the carbon material in a solvent while acting (for example, adsorbing) the dispersant on the carbon material.
- a disperser usually used for pigment dispersion or the like can be used.
- mixers such as dispersers, homomixers, planetary mixers, homogenizers ("Clearmix” manufactured by M Technique, PRIMIX “Fillmix”, etc.), paint conditioners (manufactured by Red Devil), ball mills, sand mills ( Shinmaru Enterprises "Dynomill” etc.), Attritor, Pearl Mill (Eirich “DCP Mill” etc.), Coball Mill and other media type dispersers, Wet Jet Mill (Genus “Genus PY”, Sugino Machine Media-less dispersers such as “Starburst” manufactured by Nanomizer, “Nanomizer” manufactured by Nanomizer, etc., “Claire SS-5” manufactured by M Technique,
- a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the metal agitator and vessel surface are treated with tungsten carbide spraying or resin coating is preferably used.
- ceramic beads such as glass beads, zirconia beads, and alumina beads.
- a roll mill it is preferable to use a ceramic roll. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.
- a solid binder component is added while stirring a dispersion obtained by dispersing a carbon material as a conductive aid in a solvent.
- the method of adding and dissolving is mentioned.
- the dispersion treatment may be performed again using the dispersion apparatus.
- the presence of one or more dispersants selected from organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, or triazine derivatives having basic functional groups when the carbon material as the conductive auxiliary agent is dispersed in the solvent, a part or all of the binder component may be simultaneously added to perform the dispersion treatment.
- Examples thereof include a method in which a positive electrode active material or a negative electrode active material is added and dispersed.
- one or more dispersants selected from organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, or triazine derivatives having basic functional groups (and
- a part or all of the positive electrode active material or the negative electrode active material may be added at the same time for dispersion treatment. it can.
- the above-described dispersers used for ordinary pigment dispersion and the like can be used as an apparatus for performing mixing and dispersion at this time.
- the dispersed particle size of the carbon material as the conductive assistant may be reduced to 0.03 ⁇ m or more and 2 ⁇ m or less, preferably 0.05 ⁇ m or more and 1 ⁇ m or less, more preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less. desirable. It may be difficult to produce a composition having a dispersed particle size of the carbon material as the conductive aid of less than 0.03 ⁇ m.
- the additive amount of the conductive auxiliary agent must be increased in order to reduce the resistance distribution of the electrode and reduce the resistance. There may be a problem such as disappearing.
- the dispersed particle size referred to here is a particle size (D50) that is 50% when the volume ratio of the particles is integrated from the fine particle size distribution in the volume particle size distribution.
- a particle size distribution meter such as a dynamic light scattering type particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.).
- the battery composition of the present invention is usually produced, distributed, and used as a dispersion (liquid) containing a solvent, a paste, or the like.
- a dispersion liquid
- the conductive auxiliary agent or active material and the dispersing agent are mixed in a dry powder state, the dispersing agent cannot be uniformly applied to the conductive auxiliary agent or the active material.
- the dispersant can be made to act uniformly on the conductive additive and the active material.
- the electrode mixture layer is formed on the current collector, it is preferable to apply the liquid dispersion as uniformly as possible and dry it.
- a dispersion produced by a liquid phase method may be considered as a dry powder by once removing the solvent for reasons such as transportation cost. And it is also considered that this dry powder is redispersed with an appropriate solvent and used for forming an electrode mixture layer. Therefore, the composition of the present invention is not limited to a liquid dispersion, and may be a composition in a dry powder state.
- the above-described dispersant is treated in advance.
- a carbon material as an auxiliary agent may be dispersed in a solvent.
- Conductivity treated with one or more dispersants selected from organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups examples include a method by a dry process and a method by a process in a liquid phase.
- a dispersant selected from an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, a triazine derivative having a basic functional group, and a conductive auxiliary agent A dry process with a carbon material will be described.
- the dispersing agent is allowed to act (for example, adsorb) on the surface of the carbon material while the carbon material and the dispersing agent are mixed, pulverized, or the like with a dry treatment apparatus at room temperature or under heating.
- the equipment to be used is not particularly limited.
- Media type dispersers such as paint conditioner (manufactured by Red Devil), ball mill, attritor, vibration mill, kneader, roller mill, stone mill, planetary mixer, fen Medialess dispersion / kneading machines such as Shell Mixer, Hybridizer (Nara Machinery Co., Ltd.), Mechano Micros (Nara Machinery Co., Ltd.), Mechano Fusion System AMS (Hosokawa Micron Co., Ltd.) can be used. In consideration of metal contamination and the like, it is preferable to use a medialess dispersion / kneading machine.
- the amount of dispersant selected from an acridone derivative having a basic functional group and a triazine derivative having a basic functional group depends on the specific surface area of the carbon material as the conductive auxiliary agent used, but generally 100 parts by weight of the carbon material In contrast, the dispersant is 0.5 to 40 parts by weight, preferably 1 to 35 parts by weight, and more preferably 2 to 30 parts by weight. If the amount of the dispersing agent is small, a sufficient dispersing effect cannot be obtained, and an effect of improving the wettability to the electrolytic solution and an effect of suppressing metal deposition cannot be obtained sufficiently. Moreover, even if it adds excessively, the remarkable dispersion
- a solvent may be added as long as the treated product does not become a gel.
- the effect of promoting the interaction (for example, adsorption) between the carbon material and the dispersing agent is expected by improving the wetting or (partial) dissolution of the dispersing agent by the addition of the solvent and the wetting of the carbon material with respect to the dispersing agent.
- the amount of the solvent added varies depending on the material used, but is 0.5 to 20% by weight based on the amount of the dispersant added.
- Solvents used include ketones such as methyl ethyl ketone (MEK), alcohols such as ethyl alcohol, esters such as ethyl acetate, amides such as dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP), and other ethers
- ketones such as methyl ethyl ketone (MEK)
- alcohols such as ethyl alcohol
- esters such as ethyl acetate
- amides such as dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP)
- NMP N-methyl-2-pyrrolidone
- Organic solvents such as aromatics and aromatics can be used, but are not particularly limited.
- the processing time can be arbitrarily set depending on the apparatus to be used and the desired degree of kneading. By performing these treatments, a powdery or lump-like treated product can be obtained. About the obtained processed material, you may further dry and grind
- carbon materials as conductive aids organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups are selected.
- organic dye derivatives having basic functional groups organic dye derivatives having basic functional groups
- anthraquinone derivatives having basic functional groups organic dye derivatives having basic functional groups
- acridone derivatives having basic functional groups organic dye derivatives having basic functional groups
- triazine derivatives having basic functional groups triazine derivatives having basic functional groups
- the liquid phase treatment in the present invention is at least one selected from an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group.
- the dispersant In the step of causing the dispersant to act on the carbon material (for example, adsorption), the dispersant is preferably completely or partially dissolved in the solvent. Further, it is preferable to further knead and disperse a mixture of a dispersant, a carbon material as a conductive additive and a solvent.
- Carbon materials such as carbon black, graphite, and carbon fiber often contain metallic foreign matters derived from their production processes (as line contamination and catalyst), and removing these metallic foreign matters, This is very important to prevent battery short circuit.
- a dispersant selected from organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups, Since the coagulation of the material is well loosened and the viscosity of the dispersion is low, even when the concentration of the carbon material in the dispersion is high, the metal foreign matter can be efficiently removed as compared with the case where no dispersant is added. it can. Examples of methods for removing metallic foreign substances include iron removal with a magnet, filtration, and centrifugation. The step of removing the foreign matter is preferably performed before the step of aggregating the carbon material on which the dispersant acts, such as during and / or after the step of causing the dispersant to act on the carbon material (for example, adsorption).
- examples of the solvent used include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, and phosphoric acid amides. , Sulfoxides, carboxylic acid esters, phosphate esters, ethers, nitriles and other organic solvents, and water.
- an organic solvent system (oil system)
- an organic dye derivative having a basic functional group an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a basic functional group
- One or more dispersants selected from triazine derivatives, a carbon material as a conductive additive, and an organic solvent are mixed, and the dispersant is allowed to act (for example, adsorb) on the carbon material.
- one or more dispersants selected from the above-mentioned organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, and triazine derivatives having basic functional groups It is preferable that these dispersing agents act (for example, adsorb) on the carbon material by completely or partially dissolving it in an organic solvent, adding a carbon material as a conductive aid to the solution, and mixing and dispersing it. .
- an acid as a dispersion aid.
- the acid used at this time is not particularly limited, but hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, inorganic compounds such as salts obtained by the reaction of strong acid and weak base, organic acids such as carboxylic acids, phosphoric acids and sulfonic acids are used. it can.
- a polar solvent having a relative dielectric constant of 15 or more as the solvent used in the step of causing the dispersant to act on the carbon material (for example, adsorption).
- methyl alcohol (dielectric constant: 33.1), ethyl alcohol (23.8), 2-propanol (18.3), 1-butanol (17.1), 1,2-ethanediol (38.66) ), 1,2-propanediol (32.0), 1,3-propanediol (35.0), 1,4-butanediol (31.1), diethylene glycol (31.69), 2-methoxyethanol ( 16.93), 2-ethoxyethanol (29.6), 2-aminoethanol (37.7), acetone (20.7), methyl ethyl ketone (18.51), formamide (111.0), N-methylformamide (182.4), N, N-dimethylformamide (36.71), N-methylacetamide (191.3), N, N-dimethylacetamide ( 7.78), N-methylpropionamide (172.2), N-methylpyrrolidone (32.0), hexamethylphosphoric triamide (29.6), dimethyl sulfoxide (48.9), sulf
- the relative dielectric constant is 15 or more and 200 or less, preferably 15 or more and 100 or less, more preferably 20 or more and 100 or less.
- Use polar solvents are 15 or more and 200 or less, preferably 15 or more and 100 or less, more preferably 20 or more and 100 or less.
- a solvent having a large electron-accepting effect it is preferable to include a solvent having a large electron-accepting effect. Particularly, a solvent having an acceptor number of 15 or more is preferable, but a solvent having 25 to 60 is more preferable.
- Examples of the solvent having an acceptor number of 15 or more include N, N-dimethylformamide (16.0), benzonitrile (15.5), acetonitrile (18.9), dimethyl sulfoxide (19.3), nitromethane (20 .5), chloroform (23.1), 2-propanol (33.5), ethanol (37.9), methanol (41.5), water (54.8) and the like, but are not limited thereto. .
- a solvent having a large hydrogen bonding property it is preferable to include a solvent having a large hydrogen bonding property.
- a solvent having a solubility parameter hydrogen bonding component (SP value ( ⁇ h)) of 5 (cal / cm 3 ) 1/2 or more is preferable, but 8 (cal / Cm 3 ) 1/2 or more and 20 (cal / cm 3 ) 1/2 or less are more preferable.
- solvent having a solubility parameter hydrogen bonding component (SP value ( ⁇ h)) of 5 (cal / cm 3 ) 1/2 or more examples include, for example, aniline (5.0), 2- (2-butoxyethoxy) ethane ( 5.2), diacetone alcohol (5.3), N, N-dimethylformamide (5.5), 1-pentanol (6.8), 2-ethoxyethanol (7.0), 1-butanol ( 7.7), 1-propyl alcohol (8.5), ethanol (9.5), diethylene glycol (9.7), ethanolamine (10.4), methanol (10.9), 1,2-propanediol (11.4), 1,2-ethanediol (12.7), water (16.7) and the like, but are not limited thereto.
- SP value ( ⁇ h) solubility parameter hydrogen bonding component
- the solvent to be used preferably contains a protic polar solvent.
- a protic polar solvent include, for example, alcohols and glycols having a hydroxyl group, and amide solvents in which nitrogen is monoalkylated, such as N-methylformamide, N-methylacetamide, and N-methylpropionamide. , And water, but are not limited thereto.
- organic solvents may be used alone or in combination of two or more.
- a solvent with a large acceptor number a solvent with a high hydrogen bonding component (SP value ( ⁇ h)) with a solubility parameter, or a combination of a protic solvent and a solvent with a large relative permittivity, or a relative permittivity and an acceptor. It is preferable to use a protic solvent having a large number of solubility parameters and a hydrogen bonding component (SP value ( ⁇ h)).
- a disperser usually used for pigment dispersion or the like can be used as a device for causing the dispersing agent to act on the carbon material (for example, adsorption) while mixing and dispersing the carbon material in a solvent.
- a disperser usually used for pigment dispersion or the like can be used.
- mixers such as kneaders, dispersers, homomixers, planetary mixers, homogenizers ("Clearmix” manufactured by M Technique, PRIMIX “Fillmix”, etc.), paint conditioners (manufactured by Red Devil), ball mills, Media type dispersers such as sand mills (“Dynomill” manufactured by Shinmaru Enterprises, Inc.), attritors, pearl mills (“DCP mill” manufactured by Eirich), coball mills, etc.
- the apparatus to be used is not limited to these, but from the viewpoint of processing efficiency and productivity, it is preferable to use a mixer or a media-type disperser. Moreover, it is preferable to use what gave the metal mixing prevention process from an apparatus.
- a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the metal agitator and vessel surface are treated with tungsten carbide spraying or resin coating is preferably used.
- ceramic beads such as glass beads, zirconia beads, and alumina beads, and among them, the use of zirconia beads is preferable.
- a roll mill it is preferable to use a ceramic roll. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.
- the addition amount of one or more dispersants selected from an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group is 0.5 parts by weight or more and 40 parts by weight or less, preferably 1 part by weight or more, 35 parts per 100 parts by weight of the carbon material. It is not more than parts by weight, more preferably not less than 2 parts by weight and not more than 30 parts by weight.
- the carbon material concentration in the treatment liquid for performing the liquid phase treatment is 1% by weight or more and 50% by weight, although it depends on the characteristic values of the carbon material such as the specific surface area and surface functional group amount of the carbon material used. The following is preferable, and more preferably 5% by weight or more and 35% by weight or less.
- concentration of the carbon material is too low, the production efficiency is deteriorated, and when the concentration of the carbon material is too high, the viscosity at the time of treatment is remarkably increased and the handling property may be lowered.
- Examples of the step of aggregating the carbon material on which the dispersing agent has acted in the liquid to obtain the agglomerated particles include a method of heating and / or reducing the pressure of the above-mentioned treated product to distill off the solvent. Further, as a method of reducing the solubility or dispersibility of the dispersant on the carbon material surface in the solvent and aggregating, the above-described treatment slurry is agglomerated by mixing with a solvent having a relative dielectric constant of less than 15, more preferably 10 or less. And the like.
- the solvent having a relative dielectric constant of less than 15 is not particularly limited.
- methyl isobutyl ketone (relative dielectric constant: 13.1), ethyl acetate (6.0), butyl acetate (5.0),
- Examples include diethyl ether (4.2), xylene (2.3), toluene (2.2), heptane (1.9), hexane (1.9), pentane (1.8) and the like.
- the obtained processed product can be used as it is, but it is preferable to use it after washing, drying and grinding.
- an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a basic functional group an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a basic functional group
- One or more dispersants selected from triazine derivatives, a carbon material as a conductive additive, and water are mixed, and the dispersant is allowed to act (for example, adsorb) on the carbon material.
- one or more dispersants selected from an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group Alternatively, it is preferable that these dispersants act on the carbon material (for example, adsorb) by completely or partially dissolving it in an acidic aqueous solution, and adding and mixing and dispersing the carbon material as a conductive additive in the solution. .
- Water is preferably ion-exchanged water or purified water.
- the pH of the treatment liquid is preferably 1 ⁇ pH ⁇ 7, more preferably 2 ⁇ pH ⁇ 6, and particularly preferably 3 ⁇ pH ⁇ 5.
- An acid is added to make the pH of the treatment solution acidic.
- the acid is not particularly limited, and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, inorganic compounds such as salts obtained by the reaction of strong acid and weak base, organic acids such as carboxylic acids, phosphoric acids and sulfonic acids can be used. Among them, it is preferable to use an acid that decomposes or volatilizes in the drying process during electrode production.
- the amount of acid added to dissolve the dispersant having a basic functional group is preferably added in an amount of 0.1 to 10 equivalents, more preferably relative to the amount of the basic functional group contained in the dispersant. 0.5 to 5 equivalents.
- the same device as the treatment in the organic solvent system can be used. From the viewpoint of processing efficiency and productivity, it is preferable to use a mixer or a media-type disperser. Moreover, it is preferable to use what gave the metal mixing prevention process from an apparatus.
- the addition amount of one or more dispersants selected from an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group It is determined by the specific surface area of the carbon material as the conductive aid used.
- the dispersant is 0.5 to 40 parts by weight, preferably 1 to 35 parts by weight, more preferably 2 to 30 parts by weight with respect to 100 parts by weight of the carbon material. Or less.
- the amount of the dispersant is small, a sufficient dispersing effect cannot be obtained when the battery composition is obtained, and an effect of improving wettability to the electrolytic solution and an effect of suppressing metal deposition cannot be sufficiently obtained. Moreover, even if it adds excessively, the remarkable dispersion
- the carbon material concentration in the treatment liquid for performing the liquid phase treatment is 1% by weight or more and 50% by weight, although it depends on the characteristic values of the carbon material such as the specific surface area and surface functional group amount of the carbon material used. The following is preferable, and more preferably 5% by weight or more and 35% by weight or less.
- concentration of the carbon material is too low, the production efficiency is deteriorated, and when the concentration of the carbon material is too high, the viscosity at the time of treatment is remarkably increased and the handling property may be lowered.
- Examples of the step of aggregating the carbon material on which the dispersing agent has acted in the liquid to obtain aggregated particles include a method of heating and / or reducing the pressure of the above-mentioned treated product to distill off the water. Further, as a method of aggregating the dispersant on the surface of the carbon material by reducing the solubility or dispersibility in water, a method of agglomerating by neutralizing or basifying the pH of the treatment liquid may be mentioned. Among them, the method of neutralizing or basifying the pH of the treatment liquid to cause aggregation is preferable.
- a base for neutralization or basification examples include metal hydroxides such as alkali metals, salts obtained by the reaction of weak acids and strong bases, ammonia, organic amines, and the like, which exhibit basicity when dissolved in water. be able to. Among them, it is preferable to use a base that decomposes or volatilizes in the drying process during electrode production.
- the obtained processed product can be used as it is, but it is preferable to use it after washing, drying and grinding.
- Lithium secondary battery using the composition of the present invention will be described.
- the lithium secondary battery includes a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium.
- An electrode base layer may be formed between the positive electrode mixture layer and the current collector, or between the negative electrode mixture layer and the current collector.
- the material and shape of the current collector to be used are not particularly limited, and as the material, metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel are used.
- the positive electrode material aluminum is used as the negative electrode.
- the material is preferably copper.
- a flat plate foil is generally used, but a roughened surface, a perforated foil shape, and a mesh shape can also be used.
- Examples of the method for forming the electrode base layer on the current collector include a method in which the electrode base paste described above is applied to the electrode current collector and dried.
- the film thickness of the electrode underlayer is not particularly limited as long as the conductivity and adhesion are maintained, but is generally 0.05 ⁇ m or more and 20 ⁇ m or less, preferably 0.1 ⁇ m or more and 10 ⁇ m or less. It is.
- the electrode mixture layer is formed on the current collector by directly applying the electrode mixture paste described above on the current collector and drying the electrode mixture layer, and after forming the electrode base layer on the current collector.
- coating material paste and drying is mentioned.
- the electrode mixture layer is formed on the electrode foundation layer, after applying the electrode foundation paste on the current collector, the electrode mixture paste may be applied in a wet state and then dried. good.
- the thickness of the electrode mixture layer is generally 1 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 300 ⁇ m or less.
- the coating method is not particularly limited, and a known method can be used. Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method. Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application
- electrolytic solution constituting the lithium secondary battery of the present invention
- a solution in which an electrolyte containing lithium is dissolved in a non-aqueous solvent is used.
- electrolytes LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C , LiI, LiBr, LiCl, LiAlCl, LiHF 2 , LiSCN, LiBPh 4 and the like, but are not limited thereto.
- the non-aqueous solvent is not particularly limited, but carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -octanoic lactone. Lactones such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, 1,2-dibutoxyethane, etc.
- carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -octanoic lactone. Lactones such as tetrahydrofuran, 2-methyl
- esters such as methyl formate, methyl acetate and methyl propionate
- sulfoxides such as dimethyl sulfoxide and sulfolane
- nitriles such as acetonitrile.
- the above electrolyte solution can be held in a polymer matrix to form a gel polymer electrolyte.
- the polymer matrix include, but are not limited to, an acrylate resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, a polysiloxane having a polyalkylene oxide segment, and the like.
- the structure of the lithium secondary battery using the composition of the present invention is not particularly limited, but it is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary. Paper type, cylindrical type, button type, laminated Various shapes can be formed according to the purpose of use, such as a mold.
- Dispersant-treated carbon (1) 100 parts of acetylene black (denka black powder, primary particle size 35 nm, specific surface area 68 m 2 / g, manufactured by Denki Kagaku Kogyo Co., Ltd.), 3 parts of dispersant B, and N-methyl-2-pyrrolidone as a conductive aid Dispersant-treated carbon (1) was obtained by charging 0.3 part of (NMP) and treating it with an attritor.
- NMP N-methyl-2-pyrrolidone
- Dispersant-treated carbon (2) In a kneader, 100 parts of acetylene black (DENKA BLACK FX-35, primary particle size 23 nm, specific surface area 133 m 2 / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) serving as a conductive assistant, 4 parts of dispersant B, and 156 of NMP Part preparation and kneading treatment were performed. The obtained treated product was dried and pulverized to obtain dispersant-treated carbon (2).
- acetylene black acetylene black (DENKA BLACK FX-35, primary particle size 23 nm, specific surface area 133 m 2 / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) serving as a conductive assistant
- 4 parts of dispersant B, and 156 of NMP Part preparation and kneading treatment were performed. The obtained treated product was dried and pulverized to obtain dispersant-treated carbon (2).
- Dispersant-treated carbon (3) To the kneader, 100 parts of Ketjen black (EC-300J, specific surface area 800 m 2 / g, manufactured by Akzo) as a conductive auxiliary agent, 15 parts of dispersant D, and 268 of N, N-dimethylformamide (DMF) Part preparation and kneading treatment were performed. The obtained treated product was added to 770 parts of hexane and stirred, and then the aggregate was collected by filtration, dried and pulverized to obtain dispersant-treated carbon (3).
- Ketjen black EC-300J, specific surface area 800 m 2 / g, manufactured by Akzo
- DMF N, N-dimethylformamide
- Dispersant-treated carbon (4) 4 parts of Dispersant E was added to 1000 parts of purified water. While stirring and mixing with a disper, 1N hydrochloric acid aqueous solution was added to adjust the pH of the solution to about 3, and the dispersant was completely or partially dissolved. Subsequently, 100 parts of furnace black (Super-P Li, primary particle size 40 nm, specific surface area 62 m 2 / g, manufactured by TIMCAL) as a conductive auxiliary agent was added and mixed by stirring. At this time, a 1N hydrochloric acid aqueous solution was appropriately added to maintain the pH of the treatment liquid in the range of 3 to 5.
- furnace black Super-P Li, primary particle size 40 nm, specific surface area 62 m 2 / g, manufactured by TIMCAL
- Dispersant-treated carbon (5) 4 parts of Dispersant K was added to 1000 parts of purified water. While stirring and mixing with a disper, 1N hydrochloric acid aqueous solution was added to adjust the pH of the solution to about 3, and the dispersant was completely or partially dissolved. Subsequently, 100 parts of furnace black (talker black # 5400, primary particle size 21 nm, specific surface area 170 m 2 / g, manufactured by Tokai Carbon Co., Ltd.) serving as a conductive assistant was added and stirred and mixed. At this time, a 1N hydrochloric acid aqueous solution was appropriately added to maintain the pH of the treatment liquid in the range of 3 to 5.
- furnace black stalker black # 5400, primary particle size 21 nm, specific surface area 170 m 2 / g, manufactured by Tokai Carbon Co., Ltd.
- this slurry was circulated and dispersed in a sand mill whose vessel was made of ceramic using zirconia beads as a medium. During the dispersion, the mill base was stirred with a stirring blade with a magnet. Next, the obtained dispersion was passed through a 20 ⁇ m filter, and triethylamine (TEA) was added to the filtrate to adjust the pH of the liquid to 10-11. At this time, since the viscosity of the liquid rapidly increased, purified water was appropriately added. The aggregate was collected by filtration, washed with purified water, then dried and pulverized to obtain dispersant-treated carbon (5).
- TSA triethylamine
- a droplet obtained by mixing ethylene carbonate and diethyl carbonate at a ratio of 1: 1 was dropped on the pellet with a microsyringe, and the time for the droplet to penetrate the pellet was measured. This measurement was performed 5 times for each sample, and those whose average permeation time was less than 1 second was “ ⁇ ”, those that were 1 second or more and less than 5 seconds were “ ⁇ ”, 5 seconds or more, 10 seconds Those that were less than “ ⁇ ” were those that were 10 seconds or longer, and “x”.
- the results of carbon wettability evaluation are shown in Table 5 and Table 6.
- the wettability with respect to the electrolytic solution was improved as compared with the carbon not treated with the dispersant.
- acetylene black As carbon, commercially available acetylene black (Denka Black HS-100, primary particle size 48 nm, specific surface area 48 m 2 / g, Denka black powder product, primary particle size 35 nm, specific surface area 68 m 2 / g, both are electrochemical industries.
- Furnace Black (Toker Black # 5400, primary particle size 21 nm, specific surface area 170 m 2 / g, manufactured by Tokai Carbon Co., Ltd., Super-PLi, primary particle size 40 nm, specific surface area 62 m 2 / g, manufactured by TIMCAL , SUPER BLACK 205, primary particle size 42 nm, specific surface area 50 m 2 / g, manufactured by Colombian Carbon Co., or carbon nanofiber (CNF) (product name “VGCF”, fiber length 10-20 ⁇ m, fiber diameter 150 nm, ratio Any one of a surface area of 13 m 2 / g, manufactured by Showa Denko KK was used.
- CNF carbon nanofiber
- Carbon dispersion 2 In accordance with the composition shown in Table 7, 89.5 parts of N, N-dimethylformamide (DMF) and 0.5 part of Dispersant A were charged into a glass bottle and mixed by stirring to completely or partially dissolve the dispersant. Next, 10 parts of acetylene black (DENKA BLACK HS-100, primary particle size 48 nm, specific surface area 48 m 2 / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive auxiliary agent was added, and zirconia beads were further added as a medium. Dispersed with a paint shaker. The obtained dispersion was thoroughly stirred with a stirring blade equipped with a magnet, and then passed through a 20 ⁇ m filter to obtain a carbon dispersion (2).
- acetylene black DENKA BLACK HS-100, primary particle size 48 nm, specific surface area 48 m 2 / g, manufactured by Denki Kagaku Kogyo Co., Ltd.
- Carbon dispersions 8, 10, 11 According to the composition shown in Table 7 and Table 8, 88.5 to 89.7 parts of various solvents and glacial acetic acid are combined in a glass bottle, and the dispersant-treated carbons (1) to (3) shown in Tables 5 and 6 are used. Any one of them was charged from 10.3 to 11.5 parts, zirconia beads were added as a medium, and then dispersed with a paint shaker. The obtained dispersion was thoroughly stirred with a stirring blade equipped with a magnet, and then passed through a 20 ⁇ m filter to obtain various carbon dispersions.
- Carbon dispersions 21, 22 According to the composition shown in Table 9, in a glass bottle, 89.5 parts of various solvents, acetylene black (DENKA BLACK HS-100, primary particle size 48 nm, specific surface area 48 m 2 / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) 10 as a conductive auxiliary agent 10 After adding 5 parts and further adding zirconia beads as a medium, the mixture was dispersed with a paint shaker to obtain a carbon dispersion.
- acetylene black DENKA BLACK HS-100, primary particle size 48 nm, specific surface area 48 m 2 / g, manufactured by Denki Kagaku Kogyo Co., Ltd.
- Carbon dispersion 23-29 According to the composition shown in Table 9, 83.7 parts of N-methyl-2-pyrrolidone (MNP), 9.3 parts of 1,2-ethanediol (EG) and 7 parts of carbon as a conductive aid were added to a glass bottle. Further, zirconia beads were added as a medium, and then dispersed with a paint shaker to obtain a carbon dispersion.
- MNP N-methyl-2-pyrrolidone
- EG 1,2-ethanediol
- carbon carbon as a conductive aid
- acetylene black As carbon, commercially available acetylene black (Denka black powder, primary particle size 35 nm, specific surface area 68 m 2 / g, Denka black FX-35, primary particle size 23 nm, specific surface area 133 m 2 / g, both electrochemical industries Furnace Black (Toker Black # 5400, primary particle size 21 nm, specific surface area 170 m 2 / g, manufactured by Tokai Carbon Co., Ltd., Super-PLi, primary particle size 40 nm, specific surface area 62 m 2 / g, manufactured by TIMCAL , SUPER BLACK 205, primary particle size 42 nm, specific surface area 50 m 2 / g, manufactured by Colombian Carbon Co., Ltd., Ketjen Black (EC-300J, specific surface area 800 m 2 / g, manufactured by Akzo Corporation) or carbon nanofiber (CNF) ) (Product name “VGCF”, fiber length 10-20 ⁇ m, fiber diameter 1 0
- a nonionic surfactant (Emulgen A-60, polyoxyethylene derivative, manufactured by Kao Corporation) or an anionic surfactant (Demol N, ⁇ -naphthalenesulfonic acid-formalin condensate sodium) Any of salt and Kao) was used.
- Carbon dispersions 32 and 33 In accordance with the composition shown in Table 9, 89.5 parts of N-methyl-2-pyrrolidone and 0.5 part of polyvinyl pyrrolidone (weight average molecular weight: about 80,000, manufactured by Nippon Shokubai Co., Ltd.) as a dispersion resin were placed in a glass bottle and mixed and stirred. And dissolved. Next, 10 parts of carbon serving as a conductive aid was added, and zirconia beads were further added as a medium, and then dispersed with a paint shaker. The resulting dispersion was thoroughly stirred with a stirring blade equipped with a magnet, and then passed through a 20 ⁇ m filter to obtain a carbon dispersion.
- polyvinyl pyrrolidone weight average molecular weight: about 80,000, manufactured by Nippon Shokubai Co., Ltd.
- acetylene black As carbon, commercially available acetylene black (Denka Black HS-100, primary particle size 48 nm, specific surface area 48 m 2 / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) or furnace black (Toka Black # 5400, primary particle size 21 nm, specific surface area) 170 m 2 / g, manufactured by Tokai Carbon Co., Ltd.) was used.
- a droplet obtained by mixing ethylene carbonate and diethyl carbonate at a ratio of 1: 1 was dropped on the pellet with a microsyringe, and the time for the droplet to penetrate the pellet was measured. This measurement was performed 5 times for each sample, and those whose average permeation time was less than 1 second was “ ⁇ ”, those that were 1 second or more and less than 5 seconds were “ ⁇ ”, 5 seconds or more, 10 seconds Those that were less than “ ⁇ ” were those that were 10 seconds or longer, and “x”.
- the composition of the carbon dispersion is shown in Table 7, Table 8, and Table 9.
- Table 10 shows the dispersion evaluation results and the wettability evaluation results. The meanings of the abbreviations in the table are as follows.
- AN solvent acceptor number SP ( ⁇ h): hydrogen bonding component in solvent solubility parameter
- DMF N, N-dimethylformamide
- NMP N-methyl-2-pyrrolidone
- EG 1,2-ethanediol
- PG 1,2 -Propanediol addition equivalent: Acid addition equivalent to the amount of dispersant used
- the carbon dispersions (dispersions 1 to 20) using the dispersant of the present invention are obtained when only untreated carbon is dispersed in a solvent (dispersions 21 to 29) or when a general surfactant is used. Compared to (Dispersions 30, 31), it can be seen that the dispersibility is good, the viscosity is low, and the dispersion particle size is also small.
- dispersions 1 to 20 also had good dispersion stability over time (50 ° C. ⁇ 3 days), and neither thickening nor aggregation was observed.
- Example 1 90 parts of lithium cobaltate LiCoO 2 (HLC-22, average particle size 6.6 ⁇ m, specific surface area 0.62 m 2 / g, manufactured by Honjo Chemical Co., Ltd.) as a positive electrode active material, polyvinylidene fluoride (KF polymer, manufactured by Kureha Co., Ltd.) as a binder ) 4.75 parts, 21.9 parts of N, N-dimethylformamide (DMF) as a solvent were kneaded by a planetary mixer, and then 50 parts of the carbon dispersion (2) prepared previously (5 parts as carbon amount) In addition, the mixture was further kneaded to obtain a positive electrode mixture paste (see Table 11).
- KF polymer polyvinylidene fluoride
- DMF N, N-dimethylformamide
- Example 3 90 parts of lithium cobaltate LiCoO 2 (HLC-22, average particle size 6.6 ⁇ m, specific surface area 0.62 m 2 / g, manufactured by Honjo Chemical Co., Ltd.) as a positive electrode active material, polyvinylidene fluoride (KF polymer, manufactured by Kureha Co., Ltd.) as a binder ) 4.75 parts, 0.25 parts of Dispersant A, 5 parts of acetylene black (DENKA BLACK HS-100, primary particle size 48 nm, specific surface area 48 m 2 / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive assistant Then, 36.7 parts of N-methyl-2-pyrrolidone (NMP) as a solvent was kneaded with a planetary mixer, and 30 parts of NMP was further added and kneaded to obtain a positive electrode mixture paste (see Table 11).
- NMP N-methyl-2-pyrrolidone
- Example 8 90 parts of lithium cobaltate LiCoO 2 (HLC-22, average particle size 6.6 ⁇ m, specific surface area 0.62 m 2 / g, manufactured by Honjo Chemical Co., Ltd.) as a positive electrode active material, polyvinylidene fluoride (KF polymer, manufactured by Kureha Co., Ltd.) as a binder ) 4.85 parts, 21.8 parts of N-methyl-2-pyrrolidone (NMP) as a solvent were kneaded by a planetary mixer, and 50 parts of carbon dispersion (8) prepared earlier (5 parts as carbon amount) And kneaded to obtain a positive electrode mixture paste (see Table 11).
- KF polymer polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- Example 10 90 parts of lithium cobaltate LiCoO 2 (HLC-22, average particle size 6.6 ⁇ m, specific surface area 0.62 m 2 / g, manufactured by Honjo Chemical Co., Ltd.) as a positive electrode active material, polyvinylidene fluoride (KF polymer, manufactured by Kureha Co., Ltd.) as a binder ) 4.8 parts, 21.9 parts of N-methyl-2-pyrrolidone (NMP) as a solvent were kneaded with a planetary mixer, and then 50 parts of the carbon dispersion (10) prepared earlier (5 parts as carbon amount) And kneaded to obtain a positive electrode mixture paste (see Table 11).
- KF polymer polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- Example 11 90 parts of lithium cobaltate LiCoO 2 (HLC-22, average particle size 6.6 ⁇ m, specific surface area 0.62 m 2 / g, manufactured by Honjo Chemical Co., Ltd.) as a positive electrode active material, polyvinylidene fluoride (KF polymer, manufactured by Kureha Co., Ltd.) as a binder ) 4.25 parts, 22.4 parts of N-methyl-2-pyrrolidone (NMP) as a solvent were kneaded by a planetary mixer, and 50 parts of carbon dispersion (11) prepared earlier (5 parts as carbon amount) And kneaded to obtain a positive electrode mixture paste (see Table 11).
- KF polymer polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- Examples 15, 18, and 20 90 parts of lithium cobaltate LiCoO 2 (HLC-22, average particle size 6.6 ⁇ m, specific surface area 0.62 m 2 / g, manufactured by Honjo Chemical Co., Ltd.) as a positive electrode active material, N-methyl-2-pyrrolidone (NMP) as a solvent
- NMP N-methyl-2-pyrrolidone
- the previously prepared carbon dispersion (15), (18) or (20) 50 parts (5 parts as a carbon amount) and polyvinylidene fluoride (KF polymer as a binder) 4.75 parts of Kureha Co., Ltd.
- the mixture was heated under reduced pressure while kneading to distill away acetone, ethanol, or ethyl acetate to obtain a positive electrode mixture paste (see Table 11).
- Example 21 Lithium manganate LiMn 2 O 4 (CELLSEED S-LM, average particle size 12 ⁇ m, specific surface area 0.48 m 2 / g, manufactured by Nippon Chemical Industry Co., Ltd.) 85 parts as a positive electrode active material, polyvinylidene fluoride (KF polymer, Kureha) as a binder 5.6 parts), 9.36 parts of the dispersant-treated carbon (4) prepared above, and 36.7 parts of N-methyl-2-pyrrolidone (NMP) as a solvent were kneaded by a planetary mixer. Subsequently, 30 parts of NMP was added and further kneaded to obtain a positive electrode mixture paste (see Table 13).
- NMP N-methyl-2-pyrrolidone
- Lithium manganate LiMn 2 O 4 (CELLSEED S-LM, average particle size 12 ⁇ m, specific surface area 0.48 m 2 / g, manufactured by Nippon Chemical Industry Co., Ltd.) 85 parts as a positive electrode active material, polyvinylidene fluoride (KF polymer, Kureha) as a binder 6 parts) Furnace Black (Super-PLi, primary particle size 40 nm, specific surface area 62 m 2 / g, manufactured by TIMCAL) as a conductive auxiliary agent, and 9 parts N-methyl-2- 36.7 parts of pyrrolidone (NMP) was kneaded with a planetary mixer. Subsequently, 30 parts of NMP was added and further kneaded to obtain a positive electrode mixture paste (see Table 13).
- Example 22 91 parts of lithium nickelate LiNiO 2 (manufactured by Tanaka Chemical Research Co., Ltd.) as the positive electrode active material, 4.8 parts of polyvinylidene fluoride (KF polymer, manufactured by Kureha Co.) as the binder, dispersant-treated carbon (5) 4 prepared earlier 2 parts and 36.7 parts of N-methyl-2-pyrrolidone (NMP) as a solvent were kneaded by a planetary mixer. Subsequently, 30 parts of NMP was added and further kneaded to obtain a positive electrode mixture paste (see Table 13).
- KF polymer polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- Example 23 Lithium iron phosphate LiFePO 4 (average particle size 3.6 ⁇ m, specific surface area 15 m 2 / g, manufactured by TIANJIN STL ENERGY TECHNOLOGY) as positive electrode active material, 91 parts of polyvinylidene fluoride (KF polymer, manufactured by Kureha) as binder 8 parts, 30.9 parts of N-methyl-2-pyrrolidone (NMP) as a solvent were kneaded with a planetary mixer, and then 40 parts of carbon dispersion (9) prepared earlier (4 parts as carbon amount) were added. Further, the mixture was kneaded to obtain a positive electrode mixture paste (see Table 13).
- KF polymer polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- Lithium iron phosphate LiFePO 4 (average particle size 3.6 ⁇ m, specific surface area 15 m 2 / g, manufactured by TIANJIN STL ENERGY TECHNOLOGY) as positive electrode active material 91 parts, polyvinylidene fluoride (KF polymer, manufactured by Kureha) 5 parts as binder Then, 13.5 parts of N-methyl-2-pyrrolidone (NMP) as a solvent was kneaded with a planetary mixer, and then 57.1 parts of various carbon dispersions (23) prepared previously (4 parts as carbon amount) were added. Further, the mixture was kneaded to obtain a positive electrode mixture paste (see Table 13).
- NMP N-methyl-2-pyrrolidone
- Example 25 As a negative electrode active material, mesophase carbon MFC (mesophase carbon) (MCMB 6-28, average particle size 5-7 ⁇ m, specific surface area 4 m 2 / g manufactured by Osaka Gas Chemical Co., Ltd.) 93 parts, binder as carboxymethyl cellulose (Sunrose F300MC, Japan) Kneading 1 part of Paper Chemicals Co., Ltd., 3.9 parts of styrene butadiene rubber (TRD2001, manufactured by JSR) and 20 parts of the carbon dispersion (1) prepared previously (2 parts as the amount of carbon black) with a planetary mixer. After that, 48.7 parts of ion-exchanged water was added and further kneaded to obtain a negative electrode mixture paste (see Table 14).
- mesophase carbon MFC mesophase carbon MFC (mesophase carbon) (MCMB 6-28, average particle size 5-7 ⁇ m, specific surface area 4 m 2 / g manufactured by Osaka Gas Chemical Co., Ltd.) 93
- Examples 26-29, 31-33, 36, 37, 40 93 parts of mesophase carbon MFC (MCMB 6-28, average particle size 5 to 7 ⁇ m, specific surface area 4 m 2 / g made by Osaka Gas Chemical Co.) as a negative electrode active material, 4 polyvinylidene fluoride (KF polymer, made by Kureha Co.) as a binder 9 parts, 20 parts of the previously prepared carbon dispersion (2 parts as the amount of carbon black) were kneaded with a planetary mixer, then 48.7 parts of N-methyl-2-pyrrolidone was added, and further kneaded, A material paste was used. The carbon dispersion used is shown in Table 14.
- Example 30 93 parts of mesophase carbon MFC (MCMB 6-28, average particle size 5-7 ⁇ m, specific surface area 4 m 2 / g made by Osaka Gas Chemical Co.) as a negative electrode active material, 4 polyvinylidene fluoride (KF polymer, made by Kureha Co.) as a binder 7 parts, 20 parts of the previously prepared carbon dispersion (11) (2 parts as the amount of carbon black) were kneaded with a planetary mixer, and then 49.0 parts of N-methyl-2-pyrrolidone was added and further kneaded. And a negative electrode mixture paste (see Table 14).
- KF polymer polyvinylidene fluoride
- Examples 34 and 38 93 parts of mesophase carbon MFC (MCMB 6-28, average particle size 5-7 ⁇ m, specific surface area 4 m 2 / g made by Osaka Gas Chemical Co.) as a negative electrode active material, 4 polyvinylidene fluoride (KF polymer, made by Kureha Co.) as a binder 9 parts and 20 parts of the previously prepared carbon dispersion (15) or (18) (2 parts as the amount of carbon black) were kneaded by a planetary mixer. Next, 66.0 parts of N-methyl-2-pyrrolidone was added, and the mixture was heated under reduced pressure while kneading to distill off acetone or ethanol to obtain a positive electrode mixture paste (see Table 14).
- KF polymer polyvinylidene fluoride
- Examples 35 and 39 93 parts of mesophase carbon MFC (MCMB 6-28, average particle size 5-7 ⁇ m, specific surface area 4 m 2 / g made by Osaka Gas Chemical Co.) as a negative electrode active material, 4 polyvinylidene fluoride (KF polymer, made by Kureha Co.) as a binder 9 parts, 2.1 parts of the dispersant-treated carbon (4) or (5) prepared previously (2 parts as the amount of carbon black) and 26.7 parts of N-methyl-2-pyrrolidone were kneaded with a planetary mixer. did. Subsequently, 40 parts of N-methyl-2-pyrrolidone was added and further kneaded to obtain a negative electrode mixture paste (see Table 14).
- KF polymer polyvinylidene fluoride
- the positive electrode mixture paste prepared in Comparative Example 1 was applied onto the electrode underlayer with a doctor blade, and then dried under reduced pressure to produce a positive electrode mixture layer having a thickness of 100 ⁇ m.
- the rolling process by roll press etc. was not performed (refer Table 15).
- Examples 42-53, Comparative Example 23 The positive electrode mixture paste used in Examples 7-9, 11-11, and Comparative Example 11 was applied to both sides of an aluminum foil having a thickness of 20 ⁇ m, dried by heating under reduced pressure, and subjected to rolling treatment to produce a positive electrode mixture. Layers were made (see Table 17).
- the negative electrode mixture paste prepared in Comparative Example 18 was applied onto the electrode underlayer with a doctor blade, and then dried under reduced pressure to produce a negative electrode mixture layer having a thickness of 100 ⁇ m. Rolling treatment by a roll press or the like was not performed (see Table 16).
- Examples 42-53, Comparative Example 23 The negative electrode mixture paste used in Examples 26-28, 30-34, 36-38, and Example 40 and Comparative Example 20 was applied to both sides of a copper foil having a thickness of 20 ⁇ m, and then dried by heating under reduced pressure. A negative electrode mixture layer was produced by rolling (see Table 17).
- LiPF 6 was dissolved at a concentration of 1M in a solvent in which ethylene carbonate and diethyl carbonate were mixed 1: 1 as an electrolytic solution in order to evaluate battery resistance when metal components were mixed.
- Cu (BF 4 ) 2 added as a copper ion source at 10 ppm or Fe (CF 3 SO 2 ) 2 added as an iron ion source at 50 ppm was used.
- lithium manganate was used as a positive electrode active material, it showed as a relative value when the internal resistance measured value of Example 21 is set to 100. Moreover, about the case where lithium nickelate was used as a positive electrode active material, it showed as a relative value when the internal resistance measured value of Example 22 is set to 100. Moreover, about what used lithium iron phosphate as a polar active material, it showed as a relative value when the internal resistance measured value of Example 23 is set to 100.
- the charge / discharge cycle could be repeated stably for 20 cycles.
- the terminal of the basic functional group of the dispersing agent was a primary amine like the dispersing agent J and the dispersing agent L
- the capacity retention rate during 20 cycles tended to increase.
- Comparative Example 23 charging / discharging became impossible in 9 cycles.
- the carbon dispersions 34 to 37 were subjected to carbon wettability evaluation after the dispersion treatment.
- the evaluation method was in accordance with the method for carbon dispersions 7 to 20 described above.
- Table 23 shows the composition of the carbon dispersion, the dispersion evaluation results, and the wettability evaluation results.
- the meanings of the abbreviations in the table are as follows.
- AN Number of solvent acceptors
- NMP N-methyl-2-pyrrolidone
- the carbon dispersion using the dispersant of the present invention is a case where only untreated carbon is dispersed in a solvent (dispersions 21 to 29) or a case where a general surfactant is used. It can be seen that the dispersibility is good, the viscosity is low, and the dispersion particle size is small as compared with (Dispersions 30, 31). Furthermore, dispersions 34 to 37 also had good dispersion stability with time (50 ° C. ⁇ 3 days), and neither thickening nor aggregation was observed.
- Example 58 (Positive electrode active material: lithium manganate) Lithium manganate LiMn 2 O 4 (CELLSEED S-LM, average particle size 12 ⁇ m, specific surface area 0.48 m 2 / g, manufactured by Nippon Chemical Industry Co., Ltd.) 85 parts as a positive electrode active material, polyvinylidene fluoride (KF polymer, Kureha) as a binder 5.6 parts) and 35 parts of the previously prepared carbon dispersion (35) were kneaded by a planetary mixer. Subsequently, an additional 55 parts of carbon dispersion (35) was added and kneaded to obtain a positive electrode mixture paste (see Table 24).
- Example 59 (Positive electrode active material: lithium nickelate) 91 parts of lithium nickelate LiNiO 2 (manufactured by Tanaka Chemical Research Co., Ltd.) as the positive electrode active material, 4.8 parts of polyvinylidene fluoride (KF polymer, manufactured by Kureha Co., Ltd.) as the binder, and N-methyl-2-pyrrolidone (NMP) as the solvent After kneading 30.9 parts with a planetary mixer, 40 parts of the previously prepared carbon dispersion (36) (4 parts as carbon amount) was added and further kneaded to obtain a positive electrode mixture paste (see Table 24). ).
- KF polymer polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- Example 60 (Positive electrode active material: lithium iron phosphate) A positive electrode mixture paste was prepared according to the method of Example 23. The carbon dispersion used at this time is shown in Table 24.
- Example 61-64 A negative electrode mixture paste was prepared according to the method of Example 26. The carbon dispersion used at this time is shown in Table 25.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
この様に、とりわけ電極の内部抵抗を低減することは、大電流での放電を可能とすることや、充放電の効率を向上させる上で非常に重要な要素の一つとなっている。
また、金属箔などの電極集電体上に電極合材層を形成する場合、多数回充放電を繰り返すと、集電体と電極合材層の界面や、電極合材内部における活物質と導電助剤界面の密着性が悪化し、電池性能が低下する問題がある。これは、充放電におけるリチウムイオンのドープ、脱ドープにより活物質および電極合材層が膨張、収縮を繰り返すために、電極合材層と集電体界面および、活物質と導電助剤界面に局部的なせん断応力が発生し界面の密着性が悪化するためと考えられている。そしてこの場合も、導電助剤の分散が不十分であると、密着低下が著しくなる。これは、粗大な凝集粒子が存在すると、応力が緩和されにくくなるためであると思われる。
本発明の電池用組成物は、リチウム二次電池、ニッケル水素二次電池、ニッケルカドニウム二次電池、アルカリマンガン電池、鉛電池、燃料電池、キャパシタなどに用いることができるが、特にリチウム二次電池に用いると好適である。
また、本発明は、更に、分子量が300以下の酸を含むことを特徴とする上記の電池用組成物に関する。
また、本発明は、酸が、揮発性の酸であることを特徴とする上記の電池用組成物に関する。
また、本発明は、導電助剤としての炭素材料の分散粒径(D50)が2μm以下であること特徴とする上記の電池用組成物に関する。
また、本発明は、更に、バインダー成分を含むことを特徴とする上記の電池用組成物に関する。
また、本発明は、バインダー成分が、分子内にフッ素原子を含む高分子化合物であることを特徴とする上記の電池用組成物に関する。
また、本発明は、溶剤の比誘電率が15以上、200以下であることを特徴とする上記の電池用組成物に関する。
また、本発明は、アクセプター数が15以上、60以下の溶剤を含むことを特徴とする上記の電池用組成物に関する。
また、本発明は、プロトン性溶剤を含むことを特徴とする上記の電池用組成物に関する。
また、本発明は、プロトン性溶剤と非プロトン性溶剤の併用であることを特徴とする上記の電池用組成物に関する。
また、本発明は、更に、正極活物質または負極活物質を含むことを特徴とする上記の電池用組成物に関する。
また、本発明は、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤の存在下、導電助剤としての炭素材料を溶剤に分散してなる分散体に、正極活物質、負極活物質、またはバインダー成分を混合することを特徴とする電池用組成物の製造方法に関する。
また、本発明は、プロトン性溶剤と非プロトン性溶剤を併用した上述の組成物から、加熱および/もしくは減圧により、プロトン性溶剤を留去する電池用組成物の製造方法に関する。
また、本発明は、液相中での処理が有機溶剤系での処理であることを特徴とする上記の電池用組成物の製造方法に関する。
また、本発明は、液相中での処理が水系での処理であることを特徴とする上記の電池用組成物の製造方法に関する。
更に、本発明は、集電体上に正極合材層を有する正極と、集電体上に負極合材層を有する負極と、リチウムを含む電解質とを具備するリチウム二次電池であって、前記正極合材層と前記集電体との間、または前記負極合材層と前記集電体との間に、上記いずれかの電池用組成物を使用して電極下地層が形成されていることを特徴とするリチウム二次電池に関する。
更に、本発明は、上記の製造方法により製造された電池用組成物を用いて、電極合剤層および/もしくは電極下地層が形成されていることを特徴とするリチウム二次電池に関する。
本発明における導電助剤としては、炭素材料が最も好ましい。炭素材料としては、導電性を有する炭素材料であれば特に限定されるものではないが、グラファイト、カーボンブラック、カーボンナノチューブ、カーボンナノファイバー、カーボンファイバー、フラーレン等を単独で、もしくは2種類以上併せて使用することができる。導電性、入手の容易さ、およびコスト面から、カーボンブラックの使用が好ましい。
<分散剤>
本発明における分散剤としては、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性基官能基を有するアクリドン誘導体および、塩基性官能基を有するトリアジン誘導体の群から選ばれるものである。
とりわけ、下記一般式(1)で示されるトリアジン誘導体、または一般式(6)で示される有機色素誘導体の使用が好ましい。
Pは、一般式(2)、(3)または、一般式(4)のいずれかで示される置換基を表す。
Qは、-O-R2、-NH-R2、ハロゲン基、-X1-R1または、一般式(2)、(3)もしくは、一般式(4)のいずれかで示される置換基を表す。
R2は、水素原子、置換基を有してもよいアルキル基または、置換基を有してもよいアルケニル基もしくは、置換基を有してもよいアリール基を表す。
vは、1~10の整数を表す。
R3、R4はそれぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアリール基、またはR3、R4とで一体となって更なる窒素、酸素または硫黄原子を含む置換されていてもよい複素環残基を表す。とりわけ、水素原子であることが、電池内での金属析出を抑える効果が高いと思われ好ましい。
R5、R6、R7、R8は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいアリール基を表す。
R9は、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいアリール基を表す。
nは、1~4の整数を表す。
W1およびW2は、それぞれ独立に-O-R2、-NH-R2、ハロゲン基または、一般式(2)、(3)もしくは、一般式(4)のいずれかで示される置換基を表す。
R2は、水素原子、置換基を有してもよいアルキル基または、置換基を有してもよいアルケニル基もしくは、置換基を有してもよいアリール基を表す。
X7は-NH-または-O-を表し、X8およびX9は、それぞれ独立に-NH-、-O-、-CONH-、-SO2NH-、-CH2NH-または-CH2NHCOCH2NH-を表す。
Yは炭素数1~20で構成された、置換基を有してもよいアルキレン基、置換基を有してもよいアルケニレン基または、置換基を有してもよいアリーレン基を示す。
R10およびR11はそれぞれ独立に、有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基を表す。
一般式(6)
vは、1~10の整数を表す。
R5、R6、R7、R8は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいアリール基を表す。
R9は、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいアリール基を表す。
R12は有機色素残基、置換基を有していてもよい複素環残基、置換基を有していてもよい芳香族環残基を表す。
R12で表される有機色素残基としては、例えばジケトピロロピロール系色素、アゾ、ジスアゾ、ポリアゾ等のアゾ系色素、フタロシアニン系色素、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系色素、キナクリドン系色素、ジオキサジン系色素、ぺリノン系色素、ぺリレン系色素、チオインジゴ系色素、イソインドリン系色素、イソインドリノン系色素、キノフタロン系色素、スレン系色素、金属錯体系色素等が挙げられる。とりわけ、金属による電池の短絡を抑制する効果を高めるためには、金属錯体系色素ではない有機色素残基の使用が好ましい。
式(10) -SO2Cl
式(11) -COCl
式(12) -CH2NHCOCH2Cl
式(13) -CH2Cl
また、例えば、式(10)で示される置換基を導入する場合には、有機色素、アントラキノン、もしくはアクリドンをクロロスルホン酸に溶解して、塩化チオニル等の塩素化剤を反応させるが、このときの反応温度、反応時間等の条件により、有機色素、アントラキノン、もしくはアクリドンに導入する式(10)で示される置換基数をコントロールすることができる。
Pは、一般式(2)、(3)または、一般式(4)のいずれかで示される置換基を表す。
Qは、-O-R2、-NH-R2、ハロゲン基、-X1-R1または、一般式(2)、(3)もしくは、一般式(4)のいずれかで示される置換基を表す。
R2は、水素原子、置換基を有してもよいアルキル基または、置換基を有してもよいアルケニル基もしくは、置換基を有してもよいアリール基を表す。
本発明の電池用組成物では、炭素材料の良好な分散および分散安定性を得るために、分散助剤として酸を添加することが好ましい。このとき用いる酸としては、特に限定されないが、塩酸、硫酸、硝酸、燐酸、強酸と弱塩基の反応によって得られる塩類の無機化合物、カルボン酸類、燐酸類、スルホン酸類の様な有機酸等が使用できる。中でも、電極作製時の乾燥工程で分解または揮発する酸の使用が好ましく、分子量が300以下好ましくは200以下の酸の使用が望ましい。また、後述する電極活物質との反応性が低い酸の使用が好ましく、とりわけ有機酸類、特にカルボン酸類が好ましい。具体的には、例えば、蟻酸、エタン酸(酢酸)、フルオロ酢酸、プロピオン酸、酪酸、シュウ酸、マロン酸、琥珀酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸等が挙げられる。
本発明に使用する溶剤としては、例えば、アルコール類、グリコール類、セロソルブ類、アミノアルコール類、アミン類、ケトン類、カルボン酸アミド類、リン酸アミド類、スルホキシド類、カルボン酸エステル類、リン酸エステル類、エーテル類、ニトリル類、水等が挙げられる。
比誘電率は、溶剤の極性の強さを表す指標のひとつであり、浅原ほか編「溶剤ハンドブック」((株)講談社サイエンティフィク、1990年)等に記載されている。
アクセプター数は、各種溶剤の電子受容性の強さを測る尺度であり、値が大きいほどその溶剤の電子受容性が強いことを示す。このアクセプター数については、V.グートマン(大瀧、岡田訳)「ドナーとアクセプター」(学会出版センター(株)1983年)等に記載されている。
溶剤が有する比誘電率の大きさにもよるが、アクセプター数が15を下回る溶剤を用いると、十分な分散安定化効果が得られない場合がある。
本発明の組成物を正極合材もしくは負極合材に用いる場合は、上記分散剤、導電助剤としての炭素材料、および溶剤以外に、少なくとも正極活物質または負極活物質を含有させる。
本発明の組成物には、更に、バインダー成分を含有させることが好ましい。使用するバインダーとしては、エチレン、プロピレン、塩化ビニル、酢酸ビニル、ビニルアルコール、マレイン酸、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、アクリロニトリル、スチレン、ビニルブチラール、ビニルアセタール、ビニルピロリドン等を構成単位として含む重合体または共重合体;ポリウレタン樹脂、ポリエステル樹脂、フェノール樹脂、エポキシ樹脂、フェノキシ樹脂、尿素樹脂、メラミン樹脂、アルキッド樹脂、アクリル樹脂、ホルムアルデヒド樹脂、シリコン樹脂、フッ素樹脂;カルボキシメチルセルロースのようなセルロース樹脂;スチレン-ブタジエンゴム、フッ素ゴムのようなゴム類;ポリアニリン、ポリアセチレンのような導電性樹脂等が挙げられる。また、これらの樹脂の変性体や混合物、および共重合体でも良い。特に、耐性面から分子内にフッ素原子を含む高分子化合物、例えば、ポリフッ化ビニリデン、ポリフッ化ビニル、テトラフルオロエチレン等の使用が好ましい。
本発明の組成物は、正極合材または負極合材に用いることができる。正極合材または負極合材に用いる場合は、上記分散剤、導電助剤としての炭素材料、溶剤を含む組成物に、正極活物質または負極活物質、好ましくは更に分散助剤としての酸、およびバインダー成分を含有させた正・負極合材ペーストとして使用することが好ましい。
次に、本発明の組成物の製造方法について説明する。
本発明の組成物は、例えば、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤の存在下、導電助剤としての炭素材料を溶剤に分散し、該分散体に、必要に応じて正極活物質、負極活物質、またはバインダー成分を混合ないしは分散することにより、製造することができる。各成分の添加順序などについては、これに限定されるわけではない。また、必要に応じて溶剤を追加しても良い。
添加する酸の量としては、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体に含まれる塩基性官能基量に対して0.1~30当量添加するのが好ましく、1~20当量が更に好ましい。
また、バインダー成分を溶剤に溶解したものを事前に作製しておき、上記分散体と混合する方法が挙げられる。また、バインダー成分を上記分散体に添加した後に、上記分散装置で再度分散処理を行っても良い。
塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤により処理された導電助剤としての炭素材料を得る方法としては、乾式処理による方法および、液相中での処理による方法が挙げられる。
分散剤を炭素材料に作用(例えば吸着)させる工程としては、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤と、導電助剤としての炭素材料および、有機溶剤とを混合し、分散剤を炭素材料に作用(例えば吸着)させる。とりわけ、上述の塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤を、有機溶剤中に完全ないしは一部溶解させ、その溶液中に導電助剤としての炭素材料を添加して混合・分散することで、これら分散剤を炭素材料に作用(例えば吸着)させることが好ましい。
分散剤を炭素材料に作用(例えば吸着)させる工程としては、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤と、導電助剤としての炭素材料および、水とを混合し、分散剤を炭素材料に作用(例えば吸着)させる。とりわけ、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤を、水または、酸性水溶液に完全ないしは一部溶解させ、その溶液中に導電助剤としての炭素材料を添加して混合・分散することで、これら分散剤を炭素材料に作用(例えば吸着)させるのが好ましい。
次に、本発明の組成物を用いたリチウム二次電池について説明する。
本発明のリチウム二次電池を構成する電解液としては、リチウムを含んだ電解質を非水系の溶剤に溶解したものを用いる。電解質としては、LiBF4、LiClO4、LiPF6、LiAsF6、LiSbF6、LiCF3SO3、Li(CF3SO2)2N、LiC4F9SO3、Li(CF3SO2)3C、LiI、LiBr、LiCl、LiAlCl、LiHF2、LiSCN、LiBPh4等が挙げられるがこれらに限定されない。
以下、実施例に基づき本発明を更に詳しく説明するが、本発明は、実施例に限定されるものではない。実施例中、部は重量部を、%は重量%をそれぞれ表す。カーボン分散体の粒度分布測定には、動的光散乱方式の粒度分布計(日機装社製「マイクロトラックUPA」)を用い、体積粒度分布において、粒子径の細かいものからその粒子の体積割合を積算していったときに、50%となるところの粒子径(D50)を求めた。但し、導電助剤としてカーボンナノファイバーを用いたカーボン分散体の分散粒度は、グラインドゲージによる判定(JIS K5600-2-5に準ず)より求めた。また、電極合材ペーストの分散粒度については、グラインドゲージによる判定(JIS K5600-2-5に準ず)より求めた。
実施例で使用した分散剤について、構造を表1~表4に示した。
表5に示す組成に従ってカーボンの分散剤処理を行った。また、表6に分散剤処理の方法と、使用した処理装置を示した。
導電助剤となるアセチレンブラック(デンカブラック粉状品、一次粒径35nm、比表面積68m2/g、電気化学工業社製)100部、分散剤Bを3部および、N-メチル-2-ピロリドン(NMP)を0.3部仕込み、アトライターにて処理することで分散剤処理カーボン(1)を得た。
[分散剤処理カーボン(2)]
ニーダーに、導電助剤となるアセチレンブラック(デンカブラックFX-35、一次粒径23nm、比表面積133m2/g、電気化学工業社製)を100部、分散剤Bを4部および、NMPを156部仕込み、混練処理を行った。得られた処理物を乾燥、粉砕し、分散剤処理カーボン(2)を得た。
[分散剤処理カーボン(3)]
ニーダーに、導電助剤となるケッチェンブラック(EC-300J、比表面積800m2/g、アクゾ社製)を100部、分散剤Dを15部および、N,N-ジメチルホルムアミド(DMF)を268部仕込み、混練処理を行った。
得られた処理物をヘキサン770部中に添加して攪拌した後、凝集物を濾取、乾燥、粉砕して分散剤処理カーボン(3)を得た。
精製水1000部に分散剤Eを4部添加した。ディスパーにて攪拌混合しつつ1N塩酸水溶液を添加し、液のpHを約3とし、分散剤を完全ないしは一部溶解させた。続いて導電助剤となるファーネスブラック(Super-P Li、一次粒径40nm、比表面積62m2/g、TIMCAL社製)を100部加え攪拌混合した。このとき1N塩酸水溶液を適宜添加し、処理液のpHを3~5の範囲で維持した。
精製水1000部に分散剤Kを4部添加した。ディスパーにて攪拌混合しつつ1N塩酸水溶液を添加し、液のpHを約3とし、分散剤を完全ないしは一部溶解させた。続いて導電助剤となるファーネスブラック(トーカブラック#5400、一次粒径21nm、比表面積170m2/g、東海カーボン社製)を100部加え攪拌混合した。このとき1N塩酸水溶液を適宜添加し、処理液のpHを3~5の範囲で維持した。
次に、このスラリーをベッセルがセラミック製のサンドミルで、メディアとしてジルコニアビーズを使用して循環分散した。分散中は、ミルベースを磁石つきの攪拌翼で攪拌した。
次に、得られた分散体を20μmのフィルターを通した後、濾液にトリエチルアミン(TEA)を加え、液のpHを10~11とした。このとき液の粘度が急激に上昇するため、適宜精製水を追加した。凝集物を濾取した後、精製水で洗浄、その後、乾燥、粉砕して分散剤処理カーボン(5)を得た。
分散剤未処理の各種カーボンおよび、各種分散剤処理カーボンを80℃で10時間減圧乾燥した。続いて乾燥物をメノウ製の乳鉢で粉砕した後、更に80℃で12時間減圧乾燥した。得られた乾燥物を再度メノウ製乳鉢で粉砕した後、錠剤成型器(Specac社製)にて500kgf/cm2で荷重をかけ、カーボンのペレットを作製(直径10mm、厚0.5mm)した。このペレットにマイクロシリンジにて、エチレンカーボネートとジエチルカーボネートを1:1混合した液滴を落とし、液滴がペレットに浸透する時間を測定した。この測定を各サンプルとも5回行い、それらの平均浸透時間が1秒未満であったものを「◎」、1秒以上、5秒未満であったものを「○」、5秒以上、10秒未満であったものを「△」、10秒以上であったものを「×」とした。
カーボンの濡れ性評価の結果を表5および、表6に示した。
[カーボン分散体1、3~7、9、12~20]
表7および、表8に示す組成に従い、ガラス瓶に各種溶剤と各種酸を合わせて89.5部、分散剤A、C、F~Jまたは、L~Oのいずれか0.5部を仕込み、攪拌混合して分散剤を完全ないしは一部溶解させた。次に、導電助剤となるカーボン10部を加え、さらにメディアとしてジルコニアビーズを添加した後に、ペイントシェーカーで分散した。
得られた分散液を磁石つきの攪拌翼でよく攪拌した後、更に20μmのフィルターを通し、各種カーボン分散体を得た。
表7に示す組成に従い、ガラス瓶にN、N―ジメチルホルムアミド(DMF)89.5部および、分散剤Aを0.5部を仕込み、攪拌混合して分散剤を完全ないしは一部溶解させた。次に、導電助剤となるアセチレンブラック(デンカブラックHS-100、一次粒径48nm、比表面積48m2/g、電気化学工業社製)10部を加え、さらにメディアとしてジルコニアビーズを添加した後に、ペイントシェーカーで分散した。
得られた分散液を磁石つきの攪拌翼でよく攪拌した後、更に20μmのフィルターを通し、カーボン分散体(2)を得た。
表7および、表8に示す組成に従い、ガラス瓶に各種溶剤と氷酢酸を合わせて88.5~89.7部、表5および表6に示した分散剤処理カーボン(1)~(3)のうちのいずれかを10.3~11.5部仕込み、さらにメディアとしてジルコニアビーズを添加した後に、ペイントシェーカーで分散した。
得られた分散液を磁石つきの攪拌翼でよく攪拌した後、更に20μmのフィルターを通し、各種カーボン分散体を得た。
表9に示す組成に従い、ガラス瓶に、各種溶剤89.5部、導電助剤となるアセチレンブラック(デンカブラックHS-100、一次粒径48nm、比表面積48m2/g、電気化学工業社製)10.5部を加え、さらにメディアとしてジルコニアビーズを添加した後に、ペイントシェーカーで分散し、カーボン分散体を得た。
[カーボン分散体23-29]
表9に示す組成に従い、ガラス瓶に、N-メチル-2-ピロリドン(MNP)83.7部、1,2-エタンジオール(EG)9.3部および、導電助剤となるカーボン7部を加え、さらにメディアとしてジルコニアビーズを添加した後に、ペイントシェーカーで分散し、カーボン分散体を得た。
表9に示す組成に従い、ガラス瓶に、N-メチル-2-ピロリドン(MNP)80.5部、1,2-エタンジオール(EG)9.0部および、分散剤として界面活性剤0.5部を仕込み、混合攪拌して分散剤を溶解させた。次に、導電助剤となるアセチレンブラック(デンカブラックHS-100、一次粒径48nm、比表面積48m2/g、電気化学工業社製)10部を加え、さらにメディアとしてジルコニアビーズを添加した後に、ペイントシェーカーで分散し、カーボン分散体を得た。
表9に示す組成に従い、ガラス瓶に、N-メチル-2-ピロリドン89.5部、分散樹脂としてポリビニルピロリドン(重量平均分子量:約80000、日本触媒社製)0.5部を仕込み、混合攪拌して溶解させた。次に、導電助剤となるカーボン10部を加え、さらにメディアとしてジルコニアビーズを添加した後に、ペイントシェーカーで分散した。
得られた分散液を磁石つきの攪拌翼でよく攪拌した後、更に20μmのフィルターを通し、カーボン分散体を得た。
カーボン分散体7~20については、分散処理後のカーボンの濡れ性評価を行った。
各カーボン分散体の溶剤をエバポレーターにて減圧留去した後、得られた残渣を80℃で10時間減圧乾燥した。続いて乾燥物をメノウ製の乳鉢で粉砕した後、更に80℃で12時間減圧乾燥した。得られた乾燥物を再度メノウ製乳鉢で粉砕した後、錠剤成型器(Specac社製)にて500kgf/cm2で荷重をかけ、カーボンのペレットを作製(直径10mm、厚0.5mm)した。このペレットにマイクロシリンジにて、エチレンカーボネートとジエチルカーボネートを1:1混合した液滴を落とし、液滴がペレットに浸透する時間を測定した。この測定を各サンプルとも5回行い、それらの平均浸透時間が1秒未満であったものを「◎」、1秒以上、5秒未満であったものを「○」、5秒以上、10秒未満であったものを「△」、10秒以上であったものを「×」とした。
上記カーボン分散体の組成を表7、表8および、表9に示した。また、分散評価結果および、濡れ性評価結果を、表10に示した。なお、表中の略号の意味は以下のとおりである。
AN:溶剤のアクセプター数
SP(δh):溶剤の溶解性パラメーターにおける水素結合成分
DMF:N,N-ジメチルホルムアミド
NMP:N-メチル-2-ピロリドン
EG:1,2-エタンジオール
PG:1,2-プロパンジオール
添加当量:使用した分散剤の物質量に対する酸の添加当量
[実施例1]
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.75部、溶剤としてN,N-ジメチルホルムアミド(DMF)21.9部をプラネタリーミキサーにより混練した後に、先に調製したカーボン分散体(2)50部(カーボン量として5部)を加え、更に混練し、正極合材ペーストとした(表11を参照)。
[実施例2、4-7、9、12-14、16、17、19]
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.75部、溶剤としてN-メチル-2-ピロリドン(NMP)21.9部をプラネタリーミキサーにより混練した後に、先に調製した各種カーボン分散体50部(カーボン量として5部)を加え、更に混練し、正極合材ペーストとした。
使用したカーボン分散体は、表11に示した。
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.75部、分散剤Aを0.25部、導電助剤となるアセチレンブラック(デンカブラックHS-100、一次粒径48nm、比表面積48m2/g、電気化学工業社製)5部および、溶剤としてN-メチル-2-ピロリドン(NMP)36.7部をプラネタリーミキサーにより混練した後に、更にNMPを30部加え混練し、正極合材ペーストとした(表11を参照)。
[実施例8]
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.85部、溶剤としてN-メチル-2-ピロリドン(NMP)21.8部をプラネタリーミキサーにより混練した後に、先に調製したカーボン分散体(8)50部(カーボン量として5部)を加え、更に混練し、正極合材ペーストとした(表11を参照)。
[実施例10]
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.8部、溶剤としてN-メチル-2-ピロリドン(NMP)21.9部をプラネタリーミキサーにより混練した後に、先に調製したカーボン分散体(10)50部(カーボン量として5部)を加え、更に混練し、正極合材ペーストとした(表11を参照)。
[実施例11]
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.25部、溶剤としてN-メチル-2-ピロリドン(NMP)22.4部をプラネタリーミキサーにより混練した後に、先に調製したカーボン分散体(11)50部(カーボン量として5部)を加え、更に混練し、正極合材ペーストとした(表11を参照)。
[実施例15、18、20]
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、溶剤としてN-メチル-2-ピロリドン(NMP)21.9部をプラネタリーミキサーにより混練した後に、先に調製したカーボン分散体(15)、(18)または(20)50部(カーボン量として5部)および、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.75部を加え、更に混練した。次にNMPを40部添加した後、混練しつつ減圧加熱することによりアセトン、エタノールまたは、酢酸エチルを留去し、正極合材ペーストとした(表11を参照)。
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)5部、溶剤としてN-メチル-2-ピロリドン(NMP)24.1部をプラネタリーミキサーにより混練した後に、先に調製したカーボン分散体(22)47.6部(カーボン量として5部)を加え、更に混練し、正極合材ペーストとした(表12を参照)。
[比較例2-8]
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)5部、溶剤としてN-メチル-2-ピロリドン(NMP)0.2部および、先に調製した各種カーボン分散体21.4部(カーボン量として1.5部)を加え、プラネタリーミキサーにより混練した。続いて、先に調製した各種カーボン分散体50部(カーボン量として3.5部)を加え、更に混練し、正極合材ペーストとした。
使用したカーボン分散体は、表12に示した。
正極活物質としてコバルト酸リチウムLiCoO2(HLC-22、平均粒径6.6μm、比表面積0.62m2/g、本荘ケミカル社製)90部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.75部、溶剤としてN-メチル-2-ピロリドン(NMP)21.9部をプラネタリーミキサーにより混練した後に、先に調製した各種カーボン分散体50部(カーボン量として5部)を加え、更に混練し、正極合材ペーストとした。
使用したカーボン分散体は、表12に示した。
正極活物質としてマンガン酸リチウムLiMn2O4(CELLSEED S-LM、平均粒径12μm、比表面積0.48m2/g、日本化学工業社製)85部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)5.6部、先に調製した分散剤処理カーボン(4)9.36部および、溶剤としてN-メチル-2-ピロリドン(NMP)36.7部をプラネタリーミキサーにより混練した。続いて、NMPを30部添加して更に混練し、正極合材ペーストとした(表13を参照)。
正極活物質としてマンガン酸リチウムLiMn2O4(CELLSEED S-LM、平均粒径12μm、比表面積0.48m2/g、日本化学工業社製)85部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)6部、導電助剤となるカーボンとしてのファーネスブラック(Super-P Li、一次粒径40nm、比表面積62m2/g、TIMCAL社製)9部および、溶剤としてN-メチル-2-ピロリドン(NMP)36.7部をプラネタリーミキサーにより混練した。続いて、NMPを30部添加して更に混練し、正極合材ペーストとした(表13を参照)。
正極活物質としてニッケル酸リチウムLiNiO2(田中化学研究所社製)91部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.8部、先に調製した分散剤処理カーボン(5)4.2部および、溶剤としてN-メチル-2-ピロリドン(NMP)36.7部をプラネタリーミキサーにより混練した。続いて、NMPを30部添加して更に混練し、正極合材ペーストとした(表13を参照)。
正極活物質としてニッケル酸リチウムLiNiO2(田中化学研究所社製)91部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)5部、導電助剤としてのカーボン(トーカブラック#5400、一次粒径21nm、比表面積170m2/g、東海カーボン社製)4部および、溶剤としてN-メチル-2-ピロリドン(NMP)36.7部をプラネタリーミキサーにより混練した。続いて、NMPを30部添加して更に混練し、正極合材ペーストとした(表13を参照)。
正極活物質としてリン酸鉄リチウムLiFePO4(平均粒径3.6μm、比表面積15m2/g、TIANJIN STL ENERGY TECHNOLOGY社製)91部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.8部、溶剤としてN-メチル-2-ピロリドン(NMP)30.9部をプラネタリーミキサーにより混練した後に、先に調製した各種カーボン分散体(9)40部(カーボン量として4部)を加え、更に混練し、正極合材ペーストとした(表13を参照)。
正極活物質としてリン酸鉄リチウムLiFePO4(平均粒径3.6μm、比表面積15m2/g、TIANJIN STL ENERGY TECHNOLOGY社製)91部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)5部、溶剤としてN-メチル-2-ピロリドン(NMP)13.5部をプラネタリーミキサーにより混練した後に、先に調製した各種カーボン分散体(23)57.1部(カーボン量として4部)を加え、更に混練し、正極合材ペーストとした(表13を参照)。
[実施例25]
負極活物質として、メソフェーズカーボンMFC(mesophase carbon)(MCMB 6-28、平均粒径5~7μm、比表面積4m2/g大阪ガスケミカル社製)93部、バインダーとしてカルボキシメチルセルロース(サンローズF300MC、日本製紙ケミカル社製)1部および、スチレンブタジエンゴム(TRD2001、JSR社製)3.9部、先に調製したカーボン分散体(1)20部(カーボンブラック量として2部)をプラネタリーミキサーにより混練した後に、イオン交換水48.7部を加え、更に混練し、負極合材ペーストとした(表14を参照)。
負極活物質として、メソフェーズカーボンMFC(MCMB 6-28、平均粒径5~7μm、比表面積4m2/g大阪ガスケミカル社製)93部、バインダーとしてカルボキシメチルセルロース(サンローズF300MC、日本製紙ケミカル社製)1部および、スチレンブタジエンゴム(TRD2001、JSR社製)4部、先に調製したカーボン分散体(21)19.1部(カーボンブラック量として2部)をプラネタリーミキサーにより混練した後に、イオン交換水49.6部を加え、更に混練し、負極合材ペーストとした(表13を参照)。
負極活物質として、メソフェーズカーボンMFC(MCMB 6-28、平均粒径5~7μm、比表面積4m2/g大阪ガスケミカル社製)93部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.9部、先に調製したカーボン分散体20部(カーボンブラック量として2部)をプラネタリーミキサーにより混練した後に、N-メチル-2-ピロリドン48.7部を加え、更に混練し、負極合材ペーストとした。
使用したカーボン分散体は表14に示す。
負極活物質として、メソフェーズカーボンMFC(MCMB 6-28、平均粒径5~7μm、比表面積4m2/g大阪ガスケミカル社製)93部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.7部、先に調製したカーボン分散体(11)20部(カーボンブラック量として2部)をプラネタリーミキサーにより混練した後に、N-メチル-2-ピロリドン49.0部を加え、更に混練し、負極合材ペーストとした(表14を参照)。
[実施例34、38]
負極活物質として、メソフェーズカーボンMFC(MCMB 6-28、平均粒径5~7μm、比表面積4m2/g大阪ガスケミカル社製)93部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.9部および、先に調製したカーボン分散体(15)または(18)20部(カーボンブラック量として2部)をプラネタリーミキサーにより混練した。
次に、N-メチル-2-ピロリドン66.0部を加えた後に、混練しつつ減圧加熱することによりアセトンまたは、エタノールを留去し、正極合材ペーストとした(表14を参照)。
負極活物質として、メソフェーズカーボンMFC(MCMB 6-28、平均粒径5~7μm、比表面積4m2/g大阪ガスケミカル社製)93部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.9部、先に調製した分散剤処理カーボン(4)または(5)2.1部(カーボンブラック量として2部)および、N-メチル-2-ピロリドン26.7部をプラネタリーミキサーにより混練した。続いてN-メチル-2-ピロリドン40部を加え、更に混練し、負極合材ペーストとした(表14を参照)。
負極活物質として、メソフェーズカーボンMFC(MCMB 6-28、平均粒径5~7μm、比表面積4m2/g大阪ガスケミカル社製)93部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)5部、先に調製したカーボン分散体(22)19.1部(カーボンブラック量として2部)をプラネタリーミキサーにより混練した後に、N-メチル-2-ピロリドン49.6部を加え、更に混練し、負極合材ペーストとした(表14を参照)。
[比較例19]
負極活物質として、メソフェーズカーボンMFC(MCMB 6-28、平均粒径5~7μm、比表面積4m2/g大阪ガスケミカル社製)93部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)5部、導電助剤となるカーボンとしてファーネスブラック(トーカブラック#5400、一次粒径21nm、比表面積170m2/g、東海カーボン社製)2部および、N-メチル-2-ピロリドン26.7部をプラネタリーミキサーにより混練した。続いてN-メチル-2-ピロリドン40部を加え、更に混練し、負極合材ペーストとした(表14を参照)。
[比較例20]
負極活物質として、メソフェーズカーボンMFC(MCMB 6-28、平均粒径5~7μm、比表面積4m2/g大阪ガスケミカル社製)93部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.9部、先に調製したカーボン分散体(32)20部(カーボンブラック量として2部)をプラネタリーミキサーにより混練した後に、N-メチル-2-ピロリドン48.8部を加え、更に混練し、負極合材ペーストとした(表14を参照)。
[実施例24、41]
カーボン分散体(19)100部(カーボン量として10部)に、ポリフッ化ビニリデン(KFポリマー、クレハ社製)のN-メチル-2-ピロリドン溶液(固形分10%)100部および、N-メチル-2-ピロリドン5部を加え、高速ディスパーにて撹拌・混合し、導電性下地層用ペーストとした(表15および、表16を参照)。
[比較例15、21]
カーボン分散体(29)142.9部(カーボン量として10部)に、ポリフッ化ビニリデン(KFポリマー、クレハ社製)のN-メチル-2-ピロリドン溶液(固形分10%)100部を加え、高速ディスパーにて撹拌・混合し、導電性下地層用ペーストとした(表15および、表16を参照)。
[比較例16、22]
カーボン分散体(33)100部(カーボンブラック量として10部)に、ポリフッ化ビニリデン(KFポリマー、クレハ社製)のN-メチル-2-ピロリドン溶液(固形分10%)100部および、N-メチル-2-ピロリドン5部を加え、高速ディスパーにて撹拌・混合し、導電性下地層用ペーストとした(表15および、表16を参照)。
[実施例1-23、比較例1-14]
先に調製した正極合材ペーストを、集電体となる厚さ20μmのアルミ箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥、圧延処理して、厚さ100μmの正極合材層を作製した(表11~13を参照)。
[実施例24、比較例15、16]
先に調製した電極下地層ペーストを、厚さ20μmのアルミ箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥し、厚さ2μmの電極下地層を作製した。つづいて、電極下地層上に比較例1で調製した正極合材ペーストをドクターブレードで塗布した後、減圧加熱乾燥し、厚さ100μmの正極合材層を作製した。ロールプレス等による圧延処理は行わなかった(表15を参照)。
[実施例42-53、比較例23]
実施例7-9、実施例11-19および、比較例11で使用した正極合材ペーストを、厚さ20μmのアルミ箔の両面に塗布した後、減圧加熱乾燥し、圧延処理して正極合材層を作製した(表17を参照)。
[実施例25-40、比較例17-20]
先に調製した各種負極合材ペーストを、集電体となる厚さ20μmの銅箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥、圧延処理し、厚さ100μmの負極合材層を作製した(表14を参照)。
[実施例41、比較例21、22]
先に調製した各種電極下地層ペーストを、厚さ20μmの銅箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥し、厚さ2μmの電極下地層を作製した。次に、電極下地層上に比較例18で調製した負極合材ペーストをドクターブレードで塗布した後、減圧加熱乾燥し、厚さ100μmの負極合材層を作製した。ロールプレス等による圧延処理は行わなかった(表16を参照)。
[実施例42-53、比較例23]
実施例26-28、30-34、36-38および、実施例40と、比較例20で使用した負極合材ペーストを、厚さ20μmの銅箔の両面に塗布した後、減圧加熱乾燥し、圧延処理して負極合材層を作製した(表17を参照)。
[実施例1-24、比較例1-16]
先に作製した正極を、直径9mmに打ち抜き作用極とし、金属リチウム箔(厚さ0.15mm)を対極として、作用極および対極の間に多孔質ポリプロピレンフィルムからなるセパレーター(セルガード社製 #2400)を挿入積層し、電解液(エチレンカーボネートとジエチルカーボネートを1:1に混合した混合溶媒にLiPF6を1Mの濃度で溶解させた非水電解液)を満たして二極密閉式金属セル(宝仙社製HSフラットセル)を組み立てた。セルの組み立てはアルゴンガス置換したグローブボックス内で行い、セル組み立て後、所定の電池特性評価を行った(表18~表20、表15を参照)。
[実施例25-41、比較例17-22]
先に作製した負極を、直径9mmに打ち抜き作用極とし、金属リチウム箔(厚さ0.15mm)を対極として、作用極および対極の間に多孔質ポリプロピレンフィルムからなるセパレーター(セルガード社製 #2400)を挿入積層し、電解液(エチレンカーボネートとジエチルカーボネートを1:1に混合した混合溶媒にLiPF6を1Mの濃度で溶解させた非水電解液)を満たして二極密閉式金属セル(宝仙社製HSフラットセル)を組み立てた。セルの組み立てはアルゴンガス置換したグローブボックス内で行い、セル組み立て後、所定の電池特性評価を行った(表21、表16を参照)。
[実施例42-53、比較例23]
先に作製した正極および負極を幅54mm、長さ500mmに切り出し、ポリエチレンからなるセパレーター(膜厚25μm、幅58mm、空孔率50%)を介在させて巻回した。これを電池缶に納め、電解液を注液した。注液後、封口部を封止して電池を作製した(表17を参照)。
[充放電サイクル特性 実施例1-22、24、比較例1-13、15、16]
作製した電池評価用セルを室温(25℃)で、充電レート0.2C、1.0Cの定電流定電圧充電(上限電圧4.2V)で満充電とし、充電時と同じレートの定電流で放電下限電圧3.0Vまで放電を行う充放電を1サイクル(充放電間隔休止時間30分)とし、このサイクルを合計20サイクル行い、充放電サイクル特性評価(評価装置:北斗電工社製SM-8)を行った。また、評価後のセルを分解し、電極塗膜の外観を目視にて確認した。評価結果を表18~20および、表15に示した。
[充放電サイクル特性 実施例23、比較例14]
作製した電池評価用セルを室温(25℃)で、充電レート0.2C、1.0Cの定電流定電圧充電(上限電圧4.5V)で満充電とし、充電時と同じレートの定電流で放電下限電圧2.0Vまで放電を行う充放電を1サイクル(充放電間隔休止時間30分)とし、このサイクルを合計20サイクル行い、充放電サイクル特性評価(評価装置:北斗電工社製SM-8)を行った。また、評価後のセルを分解し、電極塗膜の外観を目視にて確認した。評価結果を表20に示した。
作製した電池評価用セルを室温(25℃)、充電レート0.2Cの定電流定電圧充電(上限電圧4.2V)で満充電とし、0.1C、0.2C、0.5C、1.0Cのレートの定電流で5秒放電後、電池電圧を測定した。電流値に対し電圧値をプロットし、得られた直線関係の傾きを内部抵抗とした。評価結果を表18~表20に示すが、正極活物質としてコバルト酸リチウムを用いた場合については、実施例7の内部抵抗測定値を100としたときの相対値として示した。正極活物質としてマンガン酸リチウムを用いた場合については、実施例21の内部抵抗測定値を100としたときの相対値として示した。また、正極活物質としてニッケル酸リチウムを用いた場合については、実施例22の内部抵抗測定値を100としたときの相対値として示した。また、極活物質としてリン酸鉄リチウムを用いたものについては、実施例23の内部抵抗測定値を100としたときの相対値として示した。
また、本発明の電極下地層を設けた電極(実施例24)では、密着性の向上が見られた(表15参照)。
[充放電サイクル特性 実施例25-41、比較例17-22]
作製した電池評価用セルを室温(25℃)、充電レート0.2C、1.0Cの定電流定電圧充電(上限電圧0.5V)で満充電とし、充電時と同じレートの定電流で電圧が1.5Vになるまで放電を行う充放電を1サイクル(充放電間隔休止時間30分)とし、このサイクルを合計20サイクル行い、充放電サイクル特性評価(評価装置:北斗電工製SM-8)を行った。また、評価後のセルを分解し、電極塗膜不良の有無を目視にて確認した。評価結果を表21、表16に示した。
また、本発明の電極下地層を設けた電極(実施例41)では、密着性の向上が見られた(表16参照)。
[充放電サイクル特性 実施例42-53、比較例23]
作製した電池を室温(25℃)、充電レート1.0Cの定電流定電圧充電(上限電圧4.0V)で満充電とし、充電時と同じレートの定電流で電圧が2.75Vになるまで放電を行う充放電を1サイクル(充放電間隔休止時間30分)とし、このサイクルを合計20サイクル以上行った。評価としては、初期放電容量と20サイクル目の放電容量とから、容量維持率を求め、容量維持率が95%以上の場合を「◎」、90%以上95%未満を「○」、85%以上90%未満を「△」、85%未満を「×」とした。評価結果を表22に示した。
[カーボン分散体34-37]
表23に示す組成に従い、導電助剤用カーボン分散体を調整した。調整方法は、上述のカーボン分散体2の方法に準じた。
カーボン分散体34~37について、分散処理後のカーボンの濡れ性評価を行った。評価方法は、上述のカーボン分散体7~20での方法に準じた。
AN:溶剤のアクセプター数
NMP:N-メチル-2-ピロリドン
更に分散体34~37は、経時分散安定性(50℃x3日)も良好で、増粘や凝集の発生は見られなかった。
[実施例54-57](正極活物質:コバルト酸リチウム)
実施例2の方法に準じて正極合材ペーストを調整した。このとき使用したカーボン分散体を表24に示した。
正極活物質としてマンガン酸リチウムLiMn2O4(CELLSEED S-LM、平均粒径12μm、比表面積0.48m2/g、日本化学工業社製)85部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)5.6部、先に調製したカーボン分散体(35)35部をプラネタリーミキサーにより混練した。続いて、カーボン分散体(35)を更に55部添加して混練し、正極合材ペーストとした(表24を参照)。
正極活物質としてニッケル酸リチウムLiNiO2(田中化学研究所社製)91部、バインダーとしてポリフッ化ビニリデン(KFポリマー、クレハ社製)4.8部、溶剤としてN-メチル-2-ピロリドン(NMP)30.9部をプラネタリーミキサーにより混練した後に、先に調製したカーボン分散体(36)40部(カーボン量として4部)を加え、更に混練し、正極合材ペーストとした(表24を参照)。
実施例23の方法に準じて正極合材ペーストを調整した。このとき使用したカーボン分散体を表24に示した。
[実施例61-64]
実施例26の方法に準じて負極合材ペーストを調整した。このとき使用したカーボン分散体を表25に示した。
先に調製した合材ペーストを使用し電極を作製した。正極は実施例1に、負極は実施例25の方法に準じて作製した。
先に作製した電極を使用して評価用のセルの組み立てを行った。正極評価用セルについては、実施例1の方法に準じた。負極評価用セルについては、実施例25の方法に準じた。
[充放電サイクル特性 実施例54-59]
実施例1の方法に準じ、充放電サイクル特性評価を行った。評価結果を表26に示した。
実施例23の方法に準じ、充放電サイクル特性評価を行った。評価結果を表26に示した。
[充放電サイクル特性 実施例61-64]
実施例25の方法に準じ、充放電サイクル特性評価を行った。評価結果を表27に示した。
Claims (28)
- 塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤と、導電助剤としての炭素材料とを含むことを特徴とする電池用組成物。
- 更に、溶剤を含むことを特徴とする請求項1記載の電池用組成物。
- 更に、分子量が300以下の酸を含むことを特徴とする請求項2記載の電池用組成物。
- 酸が揮発性であることを特徴とする請求項3記載の電池用組成物。
- 導電助剤としての炭素材料の分散粒径(D50)が2μm以下であること特徴とする請求項1ないし4いずれか記載の電池用組成物。
- 更に、バインダー成分を含むことを特徴とする請求項1ないし5いずれか記載の電池用組成物。
- バインダー成分が、分子内にフッ素原子を含む高分子化合物であることを特徴とする請求項6記載の電池用組成物。
- 溶剤の比誘電率が15以上、200以下であることを特徴とする請求項2ないし7いずれか記載の電池用組成物。
- アクセプター数が15以上、60以下の溶剤を含むことを特徴とする請求項2ないし8いずれか記載の電池用組成物。
- 溶解性パラメーターの水素結合成分(SP値(δh))が5(cal/cm3)1/2以上、20(cal/cm3)1/2以下の溶剤を含むことを特徴とする請求項2ないし9いずれか記載の電池用組成物。
- プロトン性溶剤を含むことを特徴とする請求項2ないし10いずれか記載の電池用組成物。
- 溶剤がプロトン性溶剤と非プロトン性溶剤の併用であることを特徴とする請求項2ないし11記載の電池用組成物。
- 更に、正極活物質または負極活物質を含むことを特徴とする請求項1ないし12いずれか記載の電池用組成物。
- 塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤の存在下、少なくとも導電助剤としての炭素材料を、溶剤に分散することを特徴とする電池用組成物の製造方法。
- 塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤の存在下、導電助剤としての炭素材料を溶剤に分散してなる分散体に、正極活物質、負極活物質、またはバインダー成分を分散する電池用組成物の製造方法。
- 塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤の存在下、導電助剤としての炭素材料と、正極活物質、負極活物質、またはバインダー成分を溶剤に共分散することを特徴とする電池用組成物の製造方法。
- 更に、分子量が300以下の酸の存在下で分散することを特徴とする請求項14ないし16いずれか記載の電池用組成物の製造方法。
- 請求項12および13記載の組成物から、加熱および/もしくは減圧により、プロトン性溶剤を留去することを特徴とする電池用組成物の製造方法。
- 塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤および導電助剤としての炭素材料を使用する替わりに、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤であらかじめ処理された導電助剤としての炭素材料を使用することを特徴とする請求項14ないし18いずれか記載の電池用組成物の製造方法。
- 分散剤であらかじめ処理された導電助剤としての炭素材料が、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤の存在下で乾式処理された炭素材料であることを特徴とする請求項19記載の製造方法。
- 分散剤であらかじめ処理された導電助剤としての炭素材料が、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤の存在下、液相中で処理された炭素材料であること特徴とする請求項19記載の製造方法。
- 分散剤であらかじめ処理された導電助剤としての炭素材料が、塩基性官能基を有する有機色素誘導体、塩基性官能基を有するアントラキノン誘導体、塩基性官能基を有するアクリドン誘導体、または塩基性官能基を有するトリアジン誘導体から選ばれる1種以上の分散剤と炭素材料とを液相中で混合または分散させつつ、炭素材料表面に分散剤を作用させる工程と、分散剤が作用した炭素材料を凝集させる工程を経て得られた炭素材料であること特徴とする請求項21記載の製造方法。
- 炭素材料表面に分散剤を作用させる工程中および/もしくは、分散剤が作用した炭素材料を凝集させる工程の前に、異物を除去する工程を経ることを特徴とする請求項22記載の製造方法。
- 液相中での処理が有機溶剤系での処理であることを特徴とする請求項21ないし23いずれか記載の製造方法。
- 液相中での処理が水系での処理であることを特徴とする請求項21ないし23記載の製造方法。
- 集電体上に正極合材層を有する正極と、集電体上に負極合材層を有する負極と、リチウムを含む電解質とを具備するリチウム二次電池であって、前記正極合材層または前記負極合材層が、請求項13記載の電池用組成物を使用して形成されていることを特徴とするリチウム二次電池。
- 集電体上に正極合材層を有する正極と、集電体上に負極合材層を有する負極と、リチウムを含む電解質とを具備するリチウム二次電池であって、前記正極合材層と前記集電体との間、または前記負極合材層と前記集電体との間に、請求項1ないし12いずれか記載の電池用組成物を使用して電極下地層が形成されていることを特徴とするリチウム二次電池。
- 請求項14ないし25いずれか記載の製造方法により製造された電池用組成物を使用して形成されていることを特徴とする請求項26および27記載のリチウム二次電池。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008801304331A CN102099947A (zh) | 2008-06-04 | 2008-12-22 | 电池用组合物 |
US12/737,045 US20110159360A1 (en) | 2007-06-18 | 2008-12-22 | Composition for battery |
EP08874549.2A EP2296208B1 (en) | 2008-06-04 | 2008-12-22 | Composition for battery |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008-147081 | 2008-06-04 | ||
JP2008147081A JP4420123B2 (ja) | 2007-06-18 | 2008-06-04 | 電池用組成物 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009147765A1 true WO2009147765A1 (ja) | 2009-12-10 |
Family
ID=41401563
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2008/073303 WO2009147765A1 (ja) | 2007-06-18 | 2008-12-22 | 電池用組成物 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2296208B1 (ja) |
KR (1) | KR20110040766A (ja) |
CN (1) | CN102099947A (ja) |
WO (1) | WO2009147765A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150118559A1 (en) * | 2012-04-27 | 2015-04-30 | Toyo Ink Sc Holdings Co., Ltd. | Composition for forming electrode of lithium secondary battery, electrode and lithium secondary battery |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102653644A (zh) * | 2012-04-19 | 2012-09-05 | 珠海格力新能源科技有限公司 | 一种用于电池正极片刮粉的溶液 |
JP6450555B2 (ja) * | 2013-11-12 | 2019-01-09 | 太陽インキ製造株式会社 | スラリー組成物、電極、非水電解質二次電池および非水電解質二次電極の製造方法 |
ES2799736T3 (es) | 2014-05-20 | 2020-12-21 | Hydro Quebec | Electrodo para batería fotovoltaica |
CN104078703B (zh) * | 2014-05-23 | 2015-07-22 | 南京中储新能源有限公司 | 一种碳纳米管醌正极及二次铝电池 |
WO2016114589A1 (ko) * | 2015-01-13 | 2016-07-21 | 주식회사 엘지화학 | 리튬 이차전지의 양극 형성용 조성물의 제조방법, 및 이를 이용하여 제조한 양극 및 리튬 이차전지 |
KR101773698B1 (ko) | 2015-01-13 | 2017-08-31 | 주식회사 엘지화학 | 리튬 이차전지의 양극 형성용 조성물의 제조방법, 및 이를 이용하여 제조한 양극 및 리튬 이차전지 |
KR20160139240A (ko) | 2015-05-27 | 2016-12-07 | 주식회사 엘지화학 | 전극 합제, 이의 제조방법 및 이를 포함하는 이차전지 |
CN105552375A (zh) * | 2015-12-18 | 2016-05-04 | 山东精工电子科技有限公司 | 一种锂电池用碳纳米管浆料及其制备方法 |
KR102143953B1 (ko) | 2016-03-24 | 2020-08-12 | 주식회사 엘지화학 | 이차전지의 양극 형성용 조성물 및 이를 이용하여 제조한 이차전지용 양극 및 이차전지 |
WO2019205080A1 (en) * | 2018-04-27 | 2019-10-31 | Dow Global Technologies Llc | Solvent systems for use in lithium ion battery production |
CN109638212A (zh) * | 2018-11-20 | 2019-04-16 | 东莞锂威能源科技有限公司 | 一种高倍率快充锂离子电池 |
KR102556930B1 (ko) | 2019-02-26 | 2023-07-19 | 비와이케이-케미 게엠베하 | 빗모양 공중합체를 포함하는 조성물 |
CN110473653B (zh) * | 2019-07-26 | 2021-01-05 | 深圳烯湾科技有限公司 | 高碳含量的碳纳米管导电浆料及其制备方法 |
Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5462227A (en) | 1977-10-28 | 1979-05-19 | Toyo Ink Mfg Co Ltd | Phthalocyanine pigment composition |
JPS56118462A (en) | 1980-02-25 | 1981-09-17 | Toyo Ink Mfg Co Ltd | Pigment composition |
JPS56166266A (en) | 1980-05-23 | 1981-12-21 | Toyo Ink Mfg Co Ltd | Dispersing method of pigment |
JPS6088185A (ja) | 1983-10-18 | 1985-05-17 | 東洋インキ製造株式会社 | 顔料分散剤 |
JPS63236258A (ja) | 1987-03-20 | 1988-10-03 | Sanyo Electric Co Ltd | 非水電解液電池の正極の製造方法 |
JPS63305173A (ja) | 1987-06-05 | 1988-12-13 | Toyo Ink Mfg Co Ltd | 顔料分散剤 |
JPH032676A (ja) | 1989-05-31 | 1991-01-09 | Mitsubishi Electric Corp | 全波整流回路 |
JPH0660877A (ja) | 1991-11-14 | 1994-03-04 | Sanyo Electric Co Ltd | 液体電解質電池用電極及び非水系電解液リチウム電池用負極 |
JPH08190912A (ja) | 1995-01-12 | 1996-07-23 | Fuji Photo Film Co Ltd | 非水二次電池の負極用合剤の製造方法 |
JPH0982314A (ja) * | 1995-09-11 | 1997-03-28 | Elf Atochem Japan Kk | 電池用電極およびその製法 |
JPH11199796A (ja) | 1997-11-17 | 1999-07-27 | Toyo Ink Mfg Co Ltd | 顔料分散剤、及びそれを含有する顔料組成物 |
JP2000123823A (ja) | 1998-10-13 | 2000-04-28 | Mitsubishi Chemicals Corp | 二次電池用電極及び二次電池 |
JP2002025527A (ja) | 2000-07-03 | 2002-01-25 | Japan Storage Battery Co Ltd | 非水電解液二次電池 |
JP2002298853A (ja) | 2001-03-28 | 2002-10-11 | Tagawa Kazuo | リチウム二次電池および電気二重層キャパシタ |
JP2003157846A (ja) | 2001-11-19 | 2003-05-30 | Mikuni Color Ltd | カーボンブラックスラリー及びリチウム二次電池用電極 |
JP2003238834A (ja) * | 2002-02-22 | 2003-08-27 | Toyo Ink Mfg Co Ltd | 顔料組成物およびそれを用いた顔料分散体 |
JP2004224948A (ja) * | 2003-01-24 | 2004-08-12 | Toyo Ink Mfg Co Ltd | 乾式処理によるカーボンブラックの製造方法 |
JP2005063955A (ja) | 2003-07-28 | 2005-03-10 | Showa Denko Kk | 高密度電極及びその電極を用いた電池 |
JP2005162578A (ja) * | 2003-12-05 | 2005-06-23 | Toyo Ink Mfg Co Ltd | カーボンナノチューブ組成物、およびそれを含有するカーボンナノチューブ分散液 |
JP2005213405A (ja) * | 2004-01-30 | 2005-08-11 | Toyo Ink Mfg Co Ltd | カーボンブラック分散液の製造方法 |
JP2006516795A (ja) | 2003-04-07 | 2006-07-06 | エルジー・ケム・リミテッド | 電極活物質スラリー製造時の分散剤組成及びその利用 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6376616B1 (en) * | 1999-12-20 | 2002-04-23 | Basf Corporation | Pigment dispersants having anionic functionality for use in anodic electrocoat compositions |
JP4572023B2 (ja) * | 2000-07-11 | 2010-10-27 | 株式会社槌屋 | 着色導電ペーストおよびそれを用いる導電積層体とその製造方法 |
JP2003109875A (ja) * | 2001-10-01 | 2003-04-11 | Katsuhiko Naoi | 電極材料およびその使用 |
TW593563B (en) * | 2002-01-29 | 2004-06-21 | Toyo Ink Mfg Co | Colored composition for color filters and color filter |
JP2004307800A (ja) * | 2003-03-25 | 2004-11-04 | Nippon Paint Co Ltd | カチオン電着塗料組成物、電着浴の管理方法および電着塗装システム |
KR100644063B1 (ko) * | 2003-06-03 | 2006-11-10 | 주식회사 엘지화학 | 분산제가 화학결합된 전극용 복합 바인더 중합체 |
JP4601267B2 (ja) * | 2003-06-20 | 2010-12-22 | 東洋インキ製造株式会社 | 感光性黒色組成物、それを用いたブラックマトリックス基板およびカラーフィルタ |
JP2007521367A (ja) * | 2003-06-24 | 2007-08-02 | ピーピージー インダストリーズ オハイオ, インコーポレイテッド | ナノ微粒子相を有するマイクロ粒子の水性分散体およびそれを含有するコーティング組成物 |
US7429371B2 (en) * | 2004-03-02 | 2008-09-30 | E. I. Du Pont De Nemours And Company | Reversible oxidation of carbon nanotubes |
CN100438146C (zh) * | 2005-10-12 | 2008-11-26 | 比亚迪股份有限公司 | 锂离子电池和该电池的正极及它们的制备方法 |
KR100952277B1 (ko) * | 2007-03-05 | 2010-04-12 | 도요 잉키 세이조 가부시끼가이샤 | 전지용 조성물 |
-
2008
- 2008-12-22 EP EP08874549.2A patent/EP2296208B1/en not_active Not-in-force
- 2008-12-22 CN CN2008801304331A patent/CN102099947A/zh active Pending
- 2008-12-22 WO PCT/JP2008/073303 patent/WO2009147765A1/ja active Application Filing
- 2008-12-22 KR KR1020107028552A patent/KR20110040766A/ko not_active Application Discontinuation
Patent Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5462227A (en) | 1977-10-28 | 1979-05-19 | Toyo Ink Mfg Co Ltd | Phthalocyanine pigment composition |
JPS56118462A (en) | 1980-02-25 | 1981-09-17 | Toyo Ink Mfg Co Ltd | Pigment composition |
JPS56166266A (en) | 1980-05-23 | 1981-12-21 | Toyo Ink Mfg Co Ltd | Dispersing method of pigment |
JPS6088185A (ja) | 1983-10-18 | 1985-05-17 | 東洋インキ製造株式会社 | 顔料分散剤 |
JPS63236258A (ja) | 1987-03-20 | 1988-10-03 | Sanyo Electric Co Ltd | 非水電解液電池の正極の製造方法 |
JPS63305173A (ja) | 1987-06-05 | 1988-12-13 | Toyo Ink Mfg Co Ltd | 顔料分散剤 |
JPH032676A (ja) | 1989-05-31 | 1991-01-09 | Mitsubishi Electric Corp | 全波整流回路 |
JPH0660877A (ja) | 1991-11-14 | 1994-03-04 | Sanyo Electric Co Ltd | 液体電解質電池用電極及び非水系電解液リチウム電池用負極 |
JPH08190912A (ja) | 1995-01-12 | 1996-07-23 | Fuji Photo Film Co Ltd | 非水二次電池の負極用合剤の製造方法 |
JPH0982314A (ja) * | 1995-09-11 | 1997-03-28 | Elf Atochem Japan Kk | 電池用電極およびその製法 |
JPH11199796A (ja) | 1997-11-17 | 1999-07-27 | Toyo Ink Mfg Co Ltd | 顔料分散剤、及びそれを含有する顔料組成物 |
JP2000123823A (ja) | 1998-10-13 | 2000-04-28 | Mitsubishi Chemicals Corp | 二次電池用電極及び二次電池 |
JP2002025527A (ja) | 2000-07-03 | 2002-01-25 | Japan Storage Battery Co Ltd | 非水電解液二次電池 |
JP2002298853A (ja) | 2001-03-28 | 2002-10-11 | Tagawa Kazuo | リチウム二次電池および電気二重層キャパシタ |
JP2003157846A (ja) | 2001-11-19 | 2003-05-30 | Mikuni Color Ltd | カーボンブラックスラリー及びリチウム二次電池用電極 |
JP2003238834A (ja) * | 2002-02-22 | 2003-08-27 | Toyo Ink Mfg Co Ltd | 顔料組成物およびそれを用いた顔料分散体 |
JP2004224948A (ja) * | 2003-01-24 | 2004-08-12 | Toyo Ink Mfg Co Ltd | 乾式処理によるカーボンブラックの製造方法 |
JP2006516795A (ja) | 2003-04-07 | 2006-07-06 | エルジー・ケム・リミテッド | 電極活物質スラリー製造時の分散剤組成及びその利用 |
JP2005063955A (ja) | 2003-07-28 | 2005-03-10 | Showa Denko Kk | 高密度電極及びその電極を用いた電池 |
JP2005162578A (ja) * | 2003-12-05 | 2005-06-23 | Toyo Ink Mfg Co Ltd | カーボンナノチューブ組成物、およびそれを含有するカーボンナノチューブ分散液 |
JP2005213405A (ja) * | 2004-01-30 | 2005-08-11 | Toyo Ink Mfg Co Ltd | カーボンブラック分散液の製造方法 |
Non-Patent Citations (4)
Title |
---|
"Solvent Handbook", 1990, KODANSHA SCIENTIFIC CORPORATION |
"The Donor-Acceptor Approach to Molecular Interactions", 1983, JAPAN SCIENTIFIC SOCIETIES PRESS |
C. M. HANSEN; K. SKAARUP, J. PAINT TECH., vol. 39, 1967, pages 511 |
See also references of EP2296208A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150118559A1 (en) * | 2012-04-27 | 2015-04-30 | Toyo Ink Sc Holdings Co., Ltd. | Composition for forming electrode of lithium secondary battery, electrode and lithium secondary battery |
Also Published As
Publication number | Publication date |
---|---|
EP2296208A1 (en) | 2011-03-16 |
EP2296208A4 (en) | 2011-11-30 |
KR20110040766A (ko) | 2011-04-20 |
CN102099947A (zh) | 2011-06-15 |
EP2296208B1 (en) | 2017-05-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4420123B2 (ja) | 電池用組成物 | |
JP4240157B2 (ja) | 電池用組成物 | |
WO2009147765A1 (ja) | 電池用組成物 | |
JP5369550B2 (ja) | 電池用組成物 | |
JP5470780B2 (ja) | 電池用組成物 | |
JP5446178B2 (ja) | リチウム二次電池用正極合剤ペースト | |
JP2010086955A (ja) | 電池電極用複合材料 | |
JP5374973B2 (ja) | 負極合材およびそれを用いたリチウム二次電池 | |
JP2014194927A (ja) | 合材スラリーおよびその製造方法とそれを用いた電極、電池 | |
JP6746875B2 (ja) | 二次電池電極形成用組成物、二次電池用電極および二次電池 | |
JP6202397B2 (ja) | 二次電池電極形成用組成物、二次電池用電極および二次電池 | |
JP2009283232A (ja) | 電池用組成物の製造方法 | |
JP5071310B2 (ja) | 負極合材およびそれを用いたリチウム二次電池 | |
JP2010049873A (ja) | 電池用組成物 | |
JP2014135198A (ja) | 二次電池電極形成用組成物、二次電池用電極および二次電池 | |
JP2015125964A (ja) | 二次電池電極形成用組成物、二次電池用電極および二次電池 | |
JP5136303B2 (ja) | キャパシタ用組成物 | |
JP6003634B2 (ja) | 二次電池電極形成用組成物、二次電池電極、及び二次電池 | |
JP2013073724A (ja) | リチウムイオン二次電池正極用合材ペースト | |
JP2016181479A (ja) | リチウム二次電池用組成物 | |
JP2010049872A (ja) | 電池用組成物 | |
JP2010049874A (ja) | 電池用組成物 | |
JP6040783B2 (ja) | 二次電池電極形成用組成物、二次電池用電極および二次電池 | |
JP2015176688A (ja) | 二次電池用組成物およびそれを用いた二次電池用電極および二次電池 | |
JP2012195243A (ja) | 電池用分散剤、及びそれを用いた電池用組成物、及びリチウム二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880130433.1 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08874549 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20107028552 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2008874549 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008874549 Country of ref document: EP |