JP2014193996A - Carbon black dispersion and use thereof - Google Patents
Carbon black dispersion and use thereof Download PDFInfo
- Publication number
- JP2014193996A JP2014193996A JP2013215953A JP2013215953A JP2014193996A JP 2014193996 A JP2014193996 A JP 2014193996A JP 2013215953 A JP2013215953 A JP 2013215953A JP 2013215953 A JP2013215953 A JP 2013215953A JP 2014193996 A JP2014193996 A JP 2014193996A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- polyvinyl alcohol
- alcohol resin
- black dispersion
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006229 carbon black Substances 0.000 title claims abstract description 166
- 239000006185 dispersion Substances 0.000 title claims abstract description 101
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 96
- 229920005989 resin Polymers 0.000 claims abstract description 89
- 239000011347 resin Substances 0.000 claims abstract description 89
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 238000007127 saponification reaction Methods 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 21
- 238000003860 storage Methods 0.000 abstract description 15
- 235000019241 carbon black Nutrition 0.000 description 147
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 74
- 230000000052 comparative effect Effects 0.000 description 38
- 239000007788 liquid Substances 0.000 description 33
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 18
- -1 for example Chemical group 0.000 description 16
- 239000002033 PVDF binder Substances 0.000 description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 14
- 239000011164 primary particle Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000011282 treatment Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920002689 polyvinyl acetate Polymers 0.000 description 7
- 239000011118 polyvinyl acetate Substances 0.000 description 7
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 5
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000006232 furnace black Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical group [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 241001561902 Chaetodon citrinellus Species 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229920006369 KF polymer Polymers 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-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
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 101000713585 Homo sapiens Tubulin beta-4A chain Proteins 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 102100036788 Tubulin beta-4A chain Human genes 0.000 description 1
- 229920002310 Welan gum Polymers 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000011029 spinel Chemical group 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、分散性、貯蔵安定性に優れたカーボンブラック分散液に関する。また、該分散液を使用した電池電極合材層およびリチウムイオン二次電池に関する。 The present invention relates to a carbon black dispersion excellent in dispersibility and storage stability. The present invention also relates to a battery electrode mixture layer and a lithium ion secondary battery using the dispersion.
電池分野において、カーボンブラックは、導電助剤として広く用いられているが、電池電極合材層を形成する際、生産プロセスを効率化して短縮するためには、カーボンブラックを溶剤中に、いかに高濃度かつ均一に分散して、容易に塗工可能とするかが重要である。 In the battery field, carbon black is widely used as a conductive additive, but when forming a battery electrode mixture layer, in order to shorten the production process in an efficient manner, the carbon black can be increased in a solvent. It is important to make it possible to easily disperse in concentration and uniformly.
近年、特に環境や生産コストへの配慮から、従来よりも、より高濃度かつ均一に分散されたカーボンブラック分散液を作製することによって、溶剤使用量を低減することや乾燥時の使用エネルギーを低減することが求められている。
これらの要求は、溶剤のコストや乾燥時の使用エネルギーに大きな影響があることから、使用する溶剤が高価であるほど、または、使用する溶剤が高沸点であるほど重要になる。非水系二次電池で使用されるＮ−メチル−２−ピロリドンは、一般的な溶剤と比較して高価であり、さらに２００℃以上と沸点が非常に高いため、溶剤を回収する際に多くのエネルギーを必要とすることから、分散液における溶剤使用量の低減が強く求められている。
In recent years, especially in consideration of the environment and production costs, the amount of solvent used and the energy used during drying have been reduced by producing a carbon black dispersion with a higher concentration and uniformity than before. It is requested to do.
Since these requirements have a great influence on the cost of the solvent and the energy used during drying, the more expensive the solvent used or the higher the boiling point of the solvent used, the more important. N-methyl-2-pyrrolidone used in non-aqueous secondary batteries is more expensive than common solvents and has a very high boiling point of 200 ° C. or higher. Since energy is required, reduction of the amount of solvent used in the dispersion is strongly demanded.
多量のカーボンブラックを溶剤中に分散するためには、カーボンブラックの表面に分散剤を吸着処理して分散安定な状態にすることが、特に有効な方法であり、様々な分散剤を用いたカーボンブラック分散液が提案されている。 In order to disperse a large amount of carbon black in a solvent, it is particularly effective to adsorb a dispersant on the surface of the carbon black so that the dispersion is in a stable state. Carbon using various dispersants Black dispersions have been proposed.
例えば、特許文献１、２には、カーボンブラック、未変性又は変性ポリビニルアルコール、及びＮ−メチル−２−ピロリドンを含有する塗工液が記載されており、また、特許文献１には、前記塗工液に正極活物質又は負極活物質を添加して、リチウムイオン二次電池の電極板を製造することが記載されている。しかしながら、これら特許文献１、２におけるポリビニルアルコール類は、結着剤（樹脂バインダー）として多量のポリビニルアルコール類を使用しており、ポリビニルアルコール類を分散剤として使用するという技術的思想はない。 For example, Patent Documents 1 and 2 describe a coating liquid containing carbon black, unmodified or modified polyvinyl alcohol, and N-methyl-2-pyrrolidone, and Patent Document 1 describes the coating liquid. It describes that a positive electrode active material or a negative electrode active material is added to a working solution to produce an electrode plate of a lithium ion secondary battery. However, these polyvinyl alcohols in Patent Documents 1 and 2 use a large amount of polyvinyl alcohol as a binder (resin binder), and there is no technical idea of using polyvinyl alcohol as a dispersant.
一般に、分散剤を使用してカーボンブラックを分散する場合、分散剤の量が極端に少なくなるとカーボンブラックの分散性は悪化し、逆に分散剤の量が非常に多くなると分散性は良好になるものの、電池用途で使用する場合には、抵抗値が高くなり導電性が悪化するといった電池特性に悪影響を及ぼすことが予想される。
しかしながら、高濃度かつ均一に分散されたカーボンブラック分散液を得るために、使用するカーボンブラック、溶剤種、分散剤の物理的、化学的性質はもとより、それらの量的関係についてまで詳細に検討された例は報告されておらず、Ｎ−メチル−２−ピロリドンという特定の溶剤と、ポリビニルアルコール類を分散剤として使用する場合、カーボンブラックとポリビニルアルコール類の物理的、化学的性質、さらには、それらの量的関係が、カーボンブラック分散液や電池電極合材層、電池特性へどう影響するかについては何ら検討されていないのが実状であった。
In general, when carbon black is dispersed using a dispersant, the dispersibility of the carbon black is deteriorated when the amount of the dispersant is extremely reduced, and on the contrary, the dispersibility is improved when the amount of the dispersant is extremely increased. However, when used in battery applications, it is expected to adversely affect battery characteristics such as an increase in resistance and deterioration in conductivity.
However, in order to obtain a highly concentrated and uniformly dispersed carbon black dispersion, not only the physical and chemical properties of the carbon black used, the solvent type, and the dispersant, but also their quantitative relationships have been studied in detail. In the case where a specific solvent N-methyl-2-pyrrolidone and polyvinyl alcohols are used as a dispersant, the physical and chemical properties of carbon black and polyvinyl alcohols, Actually, no consideration has been given to how these quantitative relationships affect the carbon black dispersion liquid, the battery electrode mixture layer, and the battery characteristics.
また、一般に、リチウムイオン二次電池用電極を製造する際には、電池中の結合剤に用いる高分子材料によって電極合材液の作製に用いる溶剤が決定される。現在、リチウムイオン二次電池用電極の生産においては、電極を形成するために特に好適な結合剤としてポリフッ化ビニリデンが、ポリフッ化ビニリデンを溶かすための溶剤としてＮ−メチル−２−ピロリドンが、一般に用いられている。Ｎ−メチル−２−ピロリドンは沸点が２０２℃と非常に高く、そのために、電極合材液の乾燥には多量のエネルギーと時間を費やす必要があった。この問題を解決するために、Ｎ−メチル−２−ピロリドンを溶剤とした、出来るだけ高濃度な電極合材液を得る試みが行われてきた。リチウムイオン二次電池の電極合材液用のカーボンブラック分散液に求められるもう１つの性能として、分散剤添加量は極力少ない方が望ましいことが挙げられる。これは、分散剤を添加した分だけ、電極膜における他の電極構成成分の比率が下がるためである。 Moreover, generally, when manufacturing the electrode for lithium ion secondary batteries, the solvent used for preparation of an electrode compound liquid is determined by the polymer material used for the binder in a battery. At present, in the production of electrodes for lithium ion secondary batteries, polyvinylidene fluoride is generally used as a particularly suitable binder for forming an electrode, and N-methyl-2-pyrrolidone is generally used as a solvent for dissolving polyvinylidene fluoride. It is used. Since N-methyl-2-pyrrolidone has a very high boiling point of 202 ° C., it is necessary to spend a large amount of energy and time for drying the electrode mixture liquid. In order to solve this problem, attempts have been made to obtain an electrode mixture solution having a concentration as high as possible using N-methyl-2-pyrrolidone as a solvent. Another performance required for the carbon black dispersion liquid for the electrode mixture liquid of the lithium ion secondary battery is that it is desirable that the amount of the dispersant added is as small as possible. This is because the ratio of the other electrode constituent components in the electrode film decreases by the amount of the dispersant added.
以上の状況を鑑み、本発明では、従来公知の樹脂型分散剤と比較して、得られるカーボンブラック分散液を顕著に低粘度化すること、すなわち、達成できるカーボンブラック濃度が顕著に高く、カーボンブラックの分散性と分散液の貯蔵安定性に優れた、Ｎ−メチル−２−ピロリドンを溶剤とするカーボンブラック分散液を提供することが課題である。また、均質で良好な塗膜物性と、表面抵抗の低い電池電極合材層を提供することが課題である。 In view of the above situation, in the present invention, the resulting carbon black dispersion is significantly reduced in viscosity compared to conventionally known resin-type dispersants, that is, the carbon black concentration that can be achieved is significantly higher, and carbon It is an object to provide a carbon black dispersion using N-methyl-2-pyrrolidone as a solvent, which is excellent in black dispersibility and storage stability of the dispersion. Moreover, it is a subject to provide the battery electrode compound-material layer with a uniform and favorable coating-film physical property and low surface resistance.
本発明者らは、カーボンブラック、溶剤種、分散剤の物理的、化学的性質に着目し、それらの量的関係についてまで詳細に検討した結果、カーボンブラックの比表面積と、特定のけん化度を有するポリビニルアルコール樹脂の使用量との間に分散性に大きく寄与する臨界的範囲があることを見出し、これらが一定の範囲内である場合に高濃度、低粘度、かつ長期保存安定性が良好なカーボンブラック分散液を製造できることを見出し、本発明の完成に至った。 The inventors of the present invention focused on the physical and chemical properties of carbon black, solvent species, and dispersants, and examined the quantitative relationship between them in detail. As a result, the specific surface area of carbon black and the specific saponification degree were determined. It is found that there is a critical range that greatly contributes to dispersibility with the amount of polyvinyl alcohol resin used, and when these are within a certain range, high concentration, low viscosity, and long-term storage stability are good The present inventors have found that a carbon black dispersion can be produced and have completed the present invention.
即ち、本発明の実施態様は、カーボンブラックと、分散剤としてのポリビニルアルコール樹脂と、溶剤としてのＮ−メチル−２−ピロリドンとを含んでなるカーボンブラック分散液であって、ポリビニルアルコール樹脂のけん化度が、６０〜８５ｍｏｌ％であり、カーボンブラックのＢＥＴ比表面積をＸｍ2／ｇ、カーボンブラック１ｇに対するポリビニルアルコール樹脂の添加量をａＸｇとした場合に、ａが０．０００１７≦ａ≦０．００２５６の範囲であることを特徴とするカーボンブラック分散液に関する。 That is, an embodiment of the present invention is a carbon black dispersion liquid comprising carbon black, a polyvinyl alcohol resin as a dispersant, and N-methyl-2-pyrrolidone as a solvent, wherein the polyvinyl alcohol resin is saponified. When the degree is 60 to 85 mol%, the BET specific surface area of carbon black is Xm 2 / g, and the addition amount of polyvinyl alcohol resin to 1 g of carbon black is aXg, a is 0.00017 ≦ a ≦ 0.00256 It is related with the carbon black dispersion liquid characterized by being in the range.
また、本発明の実施態様は、カーボンブラック１００重量部に対するポリビニルアルコール樹脂が０．６５重量部以上、１５重量部以下であることを特徴とする上記カーボンブラック分散液に関する。 Moreover, the embodiment of the present invention relates to the carbon black dispersion, wherein the polyvinyl alcohol resin is 0.65 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the carbon black.
また、本発明の実施態様は、カーボンブラック１００重量部に対するポリビニルアルコール樹脂が２重量部以上、８重量部以下であることを特徴とする上記カーボンブラック分散液に関する。 In addition, an embodiment of the present invention relates to the carbon black dispersion, wherein the polyvinyl alcohol resin is 2 parts by weight or more and 8 parts by weight or less with respect to 100 parts by weight of the carbon black.
また、本発明の実施態様は、上記カーボンブラック分散液に、さらに、正極活物質または負極活物質を含有してなる電池用カーボンブラック分散液に関する。 In addition, an embodiment of the present invention relates to a carbon black dispersion for a battery, wherein the carbon black dispersion further contains a positive electrode active material or a negative electrode active material.
また、本発明の実施態様は、上記カーボンブラック分散液または上記電池用カーボンブラック分散液を塗布してなる電池電極合材層に関する。 An embodiment of the present invention also relates to a battery electrode mixture layer formed by applying the carbon black dispersion or the battery carbon black dispersion.
また、本発明の実施態様は、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イオン二次電池であって、正極および負極の少なくとも一方が、上記電池電極合材層を具備してなるリチウムイオン二次電池に関する。 An embodiment of the present invention is a lithium ion 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. And at least one of a positive electrode and a negative electrode is related with the lithium ion secondary battery which comprises the said battery electrode compound-material layer.
本発明により、従来公知の樹脂型分散剤を用いた場合よりも、顕著に低粘度なカーボンブラック分散液を得ることができ、カーボンブラック濃度を高くすることが可能となる。その結果、従来よりも高濃度なカーボンブラック分散液を提供できるようになり、Ｎ−メチル−２−ピロリドン溶剤の使用量を大幅に低減できると共に、塗工した塗膜の乾燥プロセスも大幅に短縮することが出来るようになる。また、カーボンブラックの分散性と分散液の貯蔵安定性に優れた、Ｎ−メチル−２−ピロリドンを溶剤とするカーボンブラック分散液を提供することが可能となる。 According to the present invention, it is possible to obtain a carbon black dispersion liquid having a significantly lower viscosity than when a conventionally known resin-type dispersant is used, and to increase the carbon black concentration. As a result, a carbon black dispersion with a higher concentration than before can be provided, and the amount of N-methyl-2-pyrrolidone solvent used can be greatly reduced, and the drying process of the coated film can be greatly shortened. You will be able to In addition, it is possible to provide a carbon black dispersion liquid using N-methyl-2-pyrrolidone as a solvent, which is excellent in carbon black dispersibility and dispersion storage stability.
また、該分散体を用いて二次電池用電極合材液を調製した場合、低粘度であることから活物質粉体の添加や混練が容易になり、さらに、各電極成分が高濃度な電極合材液を用いても、均質で良好な塗膜を得ることが出来るため、表面抵抗の低い電池電極合材層を得る事が可能となる。 In addition, when an electrode mixture solution for a secondary battery is prepared using the dispersion, it is easy to add and knead the active material powder because of its low viscosity, and each electrode component has a high concentration. Even when a mixture solution is used, a uniform and good coating film can be obtained, and therefore a battery electrode mixture layer having a low surface resistance can be obtained.
以下、本発明の詳細を説明する。尚、本明細書では、「カーボンブラック分散液」、「電池用カーボンブラック分散液」を「分散液」、「Ｎ−メチル−２−ピロリドン」を「ＮＭＰ」と略記することがある。 Details of the present invention will be described below. In this specification, “carbon black dispersion”, “carbon black dispersion for battery” may be abbreviated as “dispersion”, and “N-methyl-2-pyrrolidone” may be abbreviated as “NMP”.
＜カーボンブラック＞
本発明に用いるカーボンブラックとしては、市販のファーネスブラック、チャンネルブラック、サーマルブラック、アセチレンブラック、ケッチェンブラックなど各種のものを用いることができる。また、通常行われている酸化処理されたカーボンブラックや、中空カーボンブラック、黒鉛化処理されたカーボンブラック、カーボンナノチューブやカーボンナノファイバーなども使用できる。
<Carbon black>
As the carbon black used in the present invention, various types such as commercially available furnace black, channel black, thermal black, acetylene black, ketjen black and the like can be used. Ordinarily oxidized carbon black, hollow carbon black, graphitized carbon black, carbon nanotube, carbon nanofiber, and the like can also be used.
カーボンブラックの酸化処理は、カーボンブラックを空気中で高温処理したり、硝酸や二酸化窒素、オゾン等で二次的に処理したりすることによって、例えばフェノール基、キノン基、カルボキシル基、カルボニル基のような酸素含有極性官能基をカーボンブラック表面に直接導入（共有結合）する処理であり、カーボンブラックの分散性を向上させるために一般的に行われている。 The oxidation treatment of carbon black is performed by treating the carbon black at a high temperature in the air or by treating it with nitric acid, nitrogen dioxide, ozone, etc., for example, phenol group, quinone group, carboxyl group, carbonyl group. This is a treatment for directly introducing (covalently bonding) such an oxygen-containing polar functional group to the surface of carbon black, and is generally performed to improve the dispersibility of carbon black.
本発明で用いるカーボンブラックは、特に限定されるものではないが、アセチレンブラックやファーネスブラックなど、高い導電性を有し、かつ工業的に生産されるカーボンブラックが好適に用いられる。 The carbon black used in the present invention is not particularly limited, but industrially produced carbon black such as acetylene black and furnace black is preferably used.
また、分散液の製造に用いるカーボンブラックの平均一次粒子径としては、一般的な分散液や塗料に用いられるカーボンブラックの平均一次粒子径範囲と同様に０．０１〜１μｍが好ましく、特に、０．０１〜０．２μｍが好ましく、０．０１〜０．１μｍがさらに好ましい。ここでいう平均一次粒子径とは、電子顕微鏡で測定された算術平均粒子径を示し、この物性値は一般にカーボンブラックの物理的特性を表すのに用いられている。 Further, the average primary particle diameter of carbon black used in the production of the dispersion is preferably 0.01 to 1 μm, particularly in the range of the average primary particle diameter of carbon black used in general dispersions and paints. 0.01 to 0.2 μm is preferable, and 0.01 to 0.1 μm is more preferable. The average primary particle size referred to here indicates an arithmetic average particle size measured with an electron microscope, and this physical property value is generally used to represent the physical characteristics of carbon black.
カーボンブラックの物理的特性を表すその他の物性値としては、ＢＥＴ比表面積やｐＨが知られている。ＢＥＴ比表面積は、窒素吸着によりＢＥＴ法で測定された比表面積（以下、単に比表面積と記載）を指し、この比表面積はカーボンブラックの表面積に対応しており、比表面積が大きいほど分散剤を必要とする量も多くなる。ｐＨはカーボンブラック表面の官能基や含有不純物の影響を受けて変化する。 As other physical property values representing the physical characteristics of carbon black, BET specific surface area and pH are known. The BET specific surface area refers to a specific surface area (hereinafter simply referred to as a specific surface area) measured by the BET method by nitrogen adsorption, and this specific surface area corresponds to the surface area of carbon black. The amount you need also increases. The pH changes under the influence of functional groups on the carbon black surface and impurities contained therein.
＜ポリビニルアルコール樹脂＞
本発明では、分散剤としてポリビニルアルコール樹脂を用いる。すなわちポリビニルアルコール樹脂をバインダーとしてではなく分散剤として使用する。本発明で用いるポリビニルアルコール樹脂の製造方法については特に制限はないが、以下、ポリ酢酸ビニルを原料とし、これをけん化することによって得られたポリビニルアルコール樹脂について記述する。
一般に、ポリビニルアルコール樹脂は、酢酸ビニルを重合させて得られたポリ酢酸ビニルを原料とし、このポリ酢酸ビニルをけん化して、アセチル基を水酸基に置換することによって得られる。この合成プロセスのために、ポリビニルアルコール樹脂はアセチル基と水酸基を有し、その比率はけん化度として表される。なお、本発明におけるけん化度とは、業界公知のけん化度の定義と同一であり、けん化によりビニルアルコール単位に変換され得る構造単位（典型的にはビニルエステル単位）とビニルアルコール単位との合計モル数に対して当該ビニルアルコール単位のモル数が占める割合（モル％）をいう。特に、ポリ酢酸ビニルを原料として用いた場合、ポリビニルアルコール樹脂中に含まれるビニルアルコール骨格に由来した水酸基数を、酢酸ビニル骨格に由来したアセチル基数とビニルアルコール骨格に由来した水酸基数の和で除した値を意味する。
<Polyvinyl alcohol resin>
In the present invention, a polyvinyl alcohol resin is used as the dispersant. That is, polyvinyl alcohol resin is used not as a binder but as a dispersant. Although there is no restriction | limiting in particular about the manufacturing method of the polyvinyl alcohol resin used by this invention, Hereinafter, the polyvinyl alcohol resin obtained by using polyvinyl acetate as a raw material and saponifying this is described.
In general, the polyvinyl alcohol resin is obtained by using polyvinyl acetate obtained by polymerizing vinyl acetate as a raw material, saponifying the polyvinyl acetate, and substituting the acetyl group with a hydroxyl group. Because of this synthesis process, the polyvinyl alcohol resin has an acetyl group and a hydroxyl group, and the ratio is expressed as the degree of saponification. The saponification degree in the present invention is the same as the definition of saponification degree known in the industry, and the total moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification. The ratio (mol%) that the number of moles of the vinyl alcohol unit occupies with respect to the number. In particular, when polyvinyl acetate is used as a raw material, the number of hydroxyl groups derived from the vinyl alcohol skeleton contained in the polyvinyl alcohol resin is divided by the sum of the number of acetyl groups derived from the vinyl acetate skeleton and the number of hydroxyl groups derived from the vinyl alcohol skeleton. Means the value.
本発明で使用するポリビニルアルコール樹脂は、ポリビニルエステル、特にポリ酢酸ビニルをけん化することによって得られるポリビニルアルコール樹脂が専ら使用されるが、これに限定されない。また、けん化度は６０〜８５ｍｏｌ％のものが使用される。上記けん化度のポリビニルアルコール樹脂であれば、各種の市販品、合成品を単独で、もしくは２種類以上併せて使用することができる。 The polyvinyl alcohol resin used in the present invention is exclusively polyvinyl alcohol resin obtained by saponifying polyvinyl ester, particularly polyvinyl acetate, but is not limited thereto. The saponification degree is 60 to 85 mol%. If it is the polyvinyl alcohol resin of the said saponification degree, various commercial products and synthetic products can be used individually or in combination of 2 or more types.
また、上記けん化度の範囲内であれば、水酸基、酢酸基以外の官能基として、例えば、アセトアセチル基、スルホン酸基、カルボキシル基、カルボニル基、アミノ基を導入されたものや、各種の塩によって変性されたもの、その他アニオンあるいはカチオン変性されたもの、アルデヒド類によってアセタール変性（ブチラール変性等）されたものなども、本発明で使用するけん化度が６０〜８５ｍｏｌ％であるポリビニルアルコール樹脂の範囲に含まれ、これらは、単独もしくは２種類以上併せて使用することができる。 Moreover, as long as it is within the above saponification degree, functional groups other than hydroxyl group and acetic acid group, for example, acetoacetyl group, sulfonic acid group, carboxyl group, carbonyl group, amino group introduced, and various salts The range of the polyvinyl alcohol resin having a saponification degree of 60 to 85 mol% used in the present invention includes those modified by the above, other modified by anion or cation, and modified by acetal (butyral modification) by aldehydes. These can be used alone or in combination of two or more.
分散剤としてのポリビニルアルコール樹脂は、平均重合度が５０〜３０００のものが好ましく、１００〜２０００のものが特に好ましく、１００〜１５００のものがさらに好ましい。 The polyvinyl alcohol resin as the dispersant preferably has an average degree of polymerization of 50 to 3000, particularly preferably 100 to 2000, and more preferably 100 to 1500.
分散剤としてのポリビニルアルコール樹脂は、ＪＩＳ Ｋ６７２６に準ずる４％水溶液粘度が２．０〜２５ｍＰａ・ｓのものが好ましく、２．０〜２０．０ｍＰａ・ｓのものがさらに好ましい。 The polyvinyl alcohol resin as the dispersant preferably has a 4% aqueous solution viscosity of 2.0 to 25 mPa · s, more preferably 2.0 to 20.0 mPa · s, according to JIS K6726.
けん化度が６０ｍｏｌ％より小さいものは、ＮＭＰに対する溶解性は非常に良好だが、カーボンブラックに対する吸着性が乏しいために分散には有効ではないと考えられ、また、けん化度が８５ｍｏｌ％より大きいものは、ＮＭＰに対してほとんど溶解、膨潤しないことから、たとえカーボンブラックに吸着されたとしても、ＮＭＰ側に高分子鎖を伸ばすことが出来ず、そのために効果的に立体反発出来ないものと推察される。これに対して、けん化度が６０〜８５ｍｏｌ％のものは、ＮＭＰに対する溶解、または膨潤性と、カーボンブラックに対する吸着性や吸着後の立体反発効果の兼合いが良好であることから、分散剤として特に有効に機能するものと考えられる。 Those having a saponification degree of less than 60 mol% are very good in solubility in NMP, but are considered to be ineffective for dispersion due to poor adsorption to carbon black, and those having a saponification degree of more than 85 mol% Since it hardly dissolves or swells in NMP, even if it is adsorbed to carbon black, the polymer chain cannot be extended to the NMP side, and therefore it is presumed that steric repulsion cannot be effectively performed. . On the other hand, those having a saponification degree of 60 to 85 mol% have a good balance between the solubility or swelling in NMP and the adsorptivity to carbon black and the steric repulsion effect after adsorption. It is considered to function particularly effectively.
上記けん化度範囲に含まれる市販のポリビニルアルコール樹脂としては、例えば、クラレポバール（クラレ社製ポリビニルアルコール樹脂）や、ゴーセノール（日本合成化学工業社製ポリビニルアルコール樹脂）、デンカポバール（電気化学工業社製）、Ｊ−ポバール（日本酢ビ・ポバール社製）などの商品名で、種々のグレードを市場より入手することが出来る。 Examples of commercially available polyvinyl alcohol resins included in the saponification degree range include Kuraray Poval (polyvinyl alcohol resin manufactured by Kuraray Co., Ltd.), Gohsenol (polyvinyl alcohol resin manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.), and Denka Poval (manufactured by Denki Kagaku Kogyo Co., Ltd.). ), J-Poval (manufactured by Nippon Vinegar Poval) and various grades can be obtained from the market.
より具体的には、クラレポバールＰＶＡ−４０３（けん化度７８．５〜８１．５ｍｏｌ％、平均重合度３００、ＪＩＳ Ｋ６７２６に準ずる液温２０℃における４％水溶液粘度２．８〜３．３ｍＰａ・ｓ）、クラレポバールＰＶＡ−５０５（けん化度７２．５〜７４．５ｍｏｌ％、平均重合度５００、４％水溶液粘度４．２〜５．０ｍＰａ・ｓ）、Ｌ−８（同６９．５〜７２．５ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度５．０〜５．８ｍＰａ・ｓ）、Ｌ−９（同６９．５〜７２．５ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度６．０〜６．５ｍＰａ・ｓ）、Ｌ−９−７８（同７６．５〜７９．０ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度６．０〜６．７ｍＰａ・ｓ）、Ｌ−１０（同７１．５〜７３．５ｍｏｌ％、平均重合度１０００以下）、Ｃ−５０６（同７４．０〜７９．０ｍｏｌ％、平均重合度６００、４％水溶液粘度４．０〜６．０ｍＰａ・ｓ）、ＫＬ−５０６（同７４．０〜８０．０ｍｏｌ％、平均重合度６００、４％水溶液粘度５．２〜６．２ｍＰａ・ｓ）、や、ゴーセノールＫＬ−０３（同７８．５〜８２．０ｍｏｌ％、平均重合度５００以下、４％水溶液粘度２．８〜３．４ｍＰａ・ｓ）、ＫＬ−０５（同７８．５〜８２．０ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度４．０〜５．０ｍＰａ・ｓ）、ＮＫ−０５Ｒ（同７１．０〜７５．０ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度４．５〜５．５ｍＰａ・ｓ）、ＫＰ−０８Ｒ（同７１．０〜７３．５ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度６．０〜８．０ｍＰａ・ｓ）等が挙げられるが、これらに限定されるものではない。 More specifically, Kuraray Poval PVA-403 (degree of saponification of 78.5 to 81.5 mol%, average degree of polymerization of 300, 4% aqueous solution viscosity at 20 ° C. according to JIS K6726 2.8 to 3.3 mPa · s ), Kuraray Poval PVA-505 (saponification degree 72.5-74.5 mol%, average polymerization degree 500, 4% aqueous solution viscosity 4.2-5.0 mPa · s), L-8 (same 69.5-72. 5 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 5.0 to 5.8 mPa · s), L-9 (69.5 to 72.5 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 6. 0 to 6.5 mPa · s), L-9-78 (76.5 to 79.0 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 6.0 to 6.7 mPa · s), L-10 ( 71.5-73.5 mol , Average polymerization degree 1000 or less), C-506 (74.0-79.0 mol%, average polymerization degree 600, 4% aqueous solution viscosity 4.0-6.0 mPa · s), KL-506 (74.0). -80.0 mol%, average polymerization degree 600, 4% aqueous solution viscosity 5.2-6.2 mPa · s), and Gohsenol KL-03 (78.5-82.0 mol%, average polymerization degree 500 or less, 4 % Aqueous solution viscosity 2.8 to 3.4 mPa · s), KL-05 (78.5 to 82.0 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 4.0 to 5.0 mPa · s), NK -05R (same 71.0-75.0 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 4.5-5.5 mPa · s), KP-08R (71.0-73.5 mol%, average polymerization) 1000 or less, 4% aqueous solution viscosity 6.0-8 0.0 mPa · s) and the like, but are not limited thereto.
＜Ｎ−メチル−２−ピロリドン＞ <N-methyl-2-pyrrolidone>
ＮＭＰは、リチウムイオン二次電池の電極製造に用いられている。本発明では、ポリビニルアルコール樹脂の分散剤としての性能、電池性能を損なわない範囲で、他の溶剤を１種類以上併用しても良いが、本発明の想定する産業上の利用可能性から、ＮＭＰを単独で用いることが好ましい。 NMP is used for manufacturing electrodes of lithium ion secondary batteries. In the present invention, one or more other solvents may be used in combination as long as the performance of the polyvinyl alcohol resin as a dispersant and the battery performance are not impaired. However, from the industrial applicability assumed by the present invention, NMP Is preferably used alone.
＜カーボンブラック分散液の製造方法＞
本発明の分散液は、ポリビニルアルコール樹脂を分散剤として用いてカーボンブラックをＮＭＰ中に分散したものである。この場合、ポリビニルアルコール樹脂とカーボンブラックを同時、または順次添加し、混合することで、ポリビニルアルコール樹脂をカーボンブラックに作用（吸着）させつつ分散する。但し、カーボンブラック分散液の製造をより容易に行うためには、ポリビニルアルコール樹脂をＮＭＰ中に溶解、膨潤、または分散させ、その後、液中にカーボンブラックを添加し、混合することでポリビニルアルコール樹脂をカーボンブラックに作用（吸着）させることが、より好ましい。また、カーボンブラック以外の粉体として、例えば二次電池用電極活物質等を添加して、電極合材液として使用する場合、ＮＭＰ中にポリビニルアルコール樹脂とカーボンブラックと電極活物質とを同時に仕込み分散処理を行っても良い。
<Method for producing carbon black dispersion>
The dispersion of the present invention is obtained by dispersing carbon black in NMP using a polyvinyl alcohol resin as a dispersant. In this case, the polyvinyl alcohol resin and the carbon black are added simultaneously or sequentially and mixed to disperse the polyvinyl alcohol resin while acting (adsorbing) on the carbon black. However, in order to more easily produce the carbon black dispersion, the polyvinyl alcohol resin is dissolved, swollen, or dispersed in NMP, and then the carbon black is added to the liquid and mixed. It is more preferable to act (adsorb) on the carbon black. Moreover, as a powder other than carbon black, for example, when an electrode active material for a secondary battery is added and used as an electrode mixture liquid, a polyvinyl alcohol resin, carbon black, and an electrode active material are simultaneously charged in NMP. Distributed processing may be performed.
分散装置としては、顔料分散等に通常用いられている分散機を使用することができる。例えば、ディスパー、ホモミキサー、プラネタリーミキサー等のミキサー類、ホモジナイザー（エム・テクニック社製「クレアミックス」、ＰＲＩＭＩＸ社「フィルミックス」等、シルバーソン社製「アブラミックス」等）類、ペイントコンディショナー（レッドデビル社製）、コロイドミル（ＰＵＣ社製「ＰＵＣコロイドミル」、ＩＫＡ社製「コロイドミルＭＫ」）類、コーンミル（ＩＫＡ社製「コーンミルＭＫＯ」等）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、コボールミル等のメディア型分散機、湿式ジェットミル（ジーナス社製「ジーナスＰＹ」、スギノマシン社製「スターバースト」、ナノマイザー社製「ナノマイザー」等）、エム・テクニック社製「クレアＳＳ−５」、奈良機械社製「ＭＩＣＲＯＳ」等のメディアレス分散機、その他ロールミル等が挙げられるが、これらに限定されるものではない。 As the dispersion device, a disperser usually used for pigment dispersion or the like can be used. For example, mixers such as dispersers, homomixers, planetary mixers, homogenizers (such as “Clairemix” manufactured by M Technique, “Fillmix” manufactured by PRIMIX, “Abramix” manufactured by Silverson, etc.), paint conditioners ( Red Devil), colloid mill ("PUC colloid mill" manufactured by PUC, "colloid mill MK" manufactured by IKA), cone mill ("Cone mill MKO" manufactured by IKA), ball mill, sand mill (Shinmaru Enterprises) "Dynomill", etc.), Attritor, Pearl Mill ("DCP Mill" manufactured by Eirich), Coball Mill and other media type dispersers, Wet Jet Mill ("Genus PY" manufactured by Genus, "Starburst" manufactured by Sugino Machine "Nanomizer" manufactured by Nanomizer ), M Technique Co., Ltd. "Claire SS-5", Nara Machinery Co., Ltd. "MICROS" media-less dispersing machine such as, but other roll mill, and the like, but is not limited to these.
次に、乾式処理により、カーボンブラックをポリビニルアルコール樹脂で表面処理した後、分散液を製造する場合について説明する。ＮＭＰ中に、下記乾式処理により得たカーボンブラックとポリビニルアルコール樹脂の混合物を添加、混合する事により、カーボンブラック分散液を得ることが出来る。ポリビニルアルコール樹脂により表面処理されたカーボンブラックを得る方法としては、乾式処理による方法が挙げられる。 Next, the case where a dispersion liquid is manufactured after surface-treating carbon black with a polyvinyl alcohol resin by dry treatment will be described. A carbon black dispersion can be obtained by adding and mixing a mixture of carbon black and polyvinyl alcohol resin obtained by the following dry treatment in NMP. Examples of a method for obtaining carbon black surface-treated with a polyvinyl alcohol resin include a dry treatment method.
本発明における乾式処理は、常温もしくは加熱下で乾式処理装置により、カーボンブラックおよびポリビニルアルコール樹脂の混合、粉砕等を行いながら、カーボンブラック表面に上記樹脂を作用（吸着）させるものである。但し、カーボンブラック表面に上記樹脂が完全に吸着されている必要はなく、ある程度均質に混合出来ていれば、実用上は問題無い場合もある。使用する装置は、特に限定されるものではく、ペイントコンディショナー（レッドデビル社製）、ボールミル、アトライター、振動ミル等のメディア型分散機、ニーダー、ローラーミル、石臼式ミル、プラネタリーミキサー、フェンシェルミキサー、ハイブリダイザー（（株）奈良機械製作所）、メカノマイクロス（（株）奈良機械製作所）、メカノフュージョンシステムＡＭＳ（ホソカワミクロン（株））等のメディアレス分散・混錬機が使用できるが、コンタミ等を考慮し、メディアレスの分散・混錬機を使用するのがより好ましい。 In the dry treatment in the present invention, the above-mentioned resin is allowed to act (adsorb) on the surface of carbon black while mixing, pulverizing, or the like of carbon black and polyvinyl alcohol resin with a dry treatment apparatus at room temperature or under heating. However, the resin does not need to be completely adsorbed on the carbon black surface, and if it can be mixed to some extent homogeneous, there may be no practical problem. 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 contamination and the like, it is more preferable to use a medialess dispersing / kneading machine.
また、このとき処理物がゲル状にならない範囲で有機溶剤を添加してもよい。溶剤の添加によるポリビニルアルコール樹脂の濡れ、または（一部）溶解、およびカーボンブラックの上記樹脂に対する濡れが向上することで、カーボンブラックと上記樹脂間相互作用の促進が期待される。このとき用いる溶剤は特に限定されるものではないが、ＮＭＰ以外を使用する場合は処理後に乾燥することが望ましい。また、有機溶剤の添加量は用いる材料により異なるが、上記樹脂の添加量に対して０．５〜１００重量％である。さらに、必要に応じて窒素ガスなどを流すことで、乾式処理装置内部を脱酸素雰囲気として処理を行っても良い。 Moreover, you may add an organic solvent in the range by which a processed material does not become a gel form at this time. It is expected that the interaction between the carbon black and the resin is promoted by improving the wetting or (partly) dissolution of the polyvinyl alcohol resin by the addition of the solvent and the wetting of the carbon black to the resin. The solvent used at this time is not particularly limited. However, when a solvent other than NMP is used, it is desirable to dry after the treatment. Moreover, although the addition amount of an organic solvent changes with materials to be used, it is 0.5 to 100 weight% with respect to the addition amount of the said resin. Further, the inside of the dry processing apparatus may be treated as a deoxygenated atmosphere by flowing nitrogen gas or the like as necessary.
乾式処理時間は、用いる装置によって、また希望とする混練度に応じて任意に設定できる。これらの乾式処理を行うことにより、粉状もしくは塊状の処理物を得ることができる。得られた処理物については、その後さらに、乾燥、粉砕しても良い。 The dry processing time can be arbitrarily set depending on the apparatus used and the desired degree of kneading. By performing these dry treatments, a powdery or lump treated product can be obtained. The obtained processed product may be further dried and pulverized.
本発明において、カーボンブラックに対する分散剤としてのポリビニルアルコール樹脂の添加量は、カーボンブラック１００重量部に対して、０．６５重量部以上、１５重量部以下が好ましく、０．６５重量部以上、１０重量部以下がより好ましく、１重量部以上、１０重量部以下がさらに好ましく、１重量部以上、８重量部以下がさらに好ましく、２重量部以上、８重量部以下が特に好ましい。 In the present invention, the addition amount of the polyvinyl alcohol resin as a dispersant for carbon black is preferably 0.65 parts by weight or more and 15 parts by weight or less, more preferably 0.65 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of carbon black. More preferred are 1 part by weight or more and 10 parts by weight or less, further preferred is 1 part by weight or more and 8 parts by weight or less, and particularly preferred is 2 parts by weight or more and 8 parts by weight or less.
カーボンブラック分散液における分散剤としてのポリビニルアルコール樹脂の添加量は、添加するカーボンブラックの比表面積やカーボンブラック粒子の分散後の平均粒径等により決定される。特にカーボンブラックの比表面積に対するポリビニルアルコール樹脂の添加量は重要であり、ポリビニルアルコール樹脂のけん化度が６０〜８５ｍｏｌ％である場合、カーボンブラックのＢＥＴ比表面積をＸｍ2／ｇ、カーボンブラック１ｇに対するポリビニルアルコール樹脂の添加量をａＸｇとした場合に、ａが０．０００１７≦ａ≦０．００２５６の範囲で、高濃度、低粘度、かつ長期保存安定性が良好なカーボンブラック分散液を製造できる臨界的範囲があることが本発明によって見出された。
更に良好な分散液や電池特性を得る観点から、０．０００１９≦ａ≦０．００２１７の範囲であることがより好ましく、０．０００２６≦ａ≦０．００１４５の範囲であることがさらに好ましく、０．０００５１≦ａ≦０．００１４５の範囲であることが特に好ましい。
このような比率で配合することにより、本発明が解決しようとする課題であるカーボンブラック分散液の低粘度化が可能となり、高濃度で分散性と貯蔵安定性に優れた分散液を得ることが容易となる。
The addition amount of the polyvinyl alcohol resin as a dispersant in the carbon black dispersion is determined by the specific surface area of the carbon black to be added, the average particle diameter after dispersion of the carbon black particles, and the like. In particular, the addition amount of the polyvinyl alcohol resin relative to the specific surface area of the carbon black is important. When the saponification degree of the polyvinyl alcohol resin is 60 to 85 mol%, the BET specific surface area of the carbon black is Xm 2 / g, and the polyvinyl relative to 1 g of the carbon black. When the amount of alcohol resin added is aXg, it is critical that a is in the range of 0.00017 ≦ a ≦ 0.00256, and a carbon black dispersion having a high concentration, low viscosity, and good long-term storage stability can be produced. A range has been found by the present invention.
From the viewpoint of obtaining better dispersion and battery characteristics, the range of 0.00019 ≦ a ≦ 0.00217 is more preferable, the range of 0.00026 ≦ a ≦ 0.00145 is more preferable, and 0 Particularly preferred is a range of .00051 ≦ a ≦ 0.00145.
By blending at such a ratio, the viscosity of the carbon black dispersion, which is a problem to be solved by the present invention, can be reduced, and a dispersion having a high concentration and excellent dispersibility and storage stability can be obtained. It becomes easy.
＜活物質＞
本発明の分散液を電池電極合材層に用いる場合は、さらに、正極活物質または負極活物質を含有させることができる。
<Active material>
When using the dispersion liquid of this invention for a battery electrode compound-material layer, a positive electrode active material or a negative electrode active material can be contained further.
リチウムイオン二次電池用の正極活物質としては、特に限定はされないが、リチウムイオンをドーピングまたはインターカレーション可能な金属酸化物、金属硫化物等の金属化合物、および導電性高分子等を使用することができる。
例えば、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｎ等の遷移金属の酸化物、リチウムとの複合酸化物、遷移金属硫化物等の無機化合物等が挙げられる。具体的には、ＭｎＯ、Ｖ2Ｏ5、Ｖ6Ｏ13、ＴｉＯ2等の遷移金属酸化物粉末、層状構造のニッケル酸リチウム、コバルト酸リチウム、マンガン酸リチウム、スピネル構造のマンガン酸リチウムなどのリチウムと遷移金属との複合酸化物粉末、オリビン構造のリン酸化合物であるリン酸鉄リチウム系材料、ＴｉＳ2、ＦｅＳなどの遷移金属硫化物粉末等が挙げられる。また、ポリアニリン、ポリアセチレン、ポリピロール、ポリチオフェン等の導電性高分子を使用することもできる。また、上記の無機化合物や有機化合物を混合して用いてもよい。
The positive electrode active material for the lithium ion secondary battery is not particularly limited, but metal oxides capable of doping or intercalating lithium ions, metal compounds such as metal sulfides, and conductive polymers are used. be able to.
Examples thereof include transition metal oxides such as Fe, Co, Ni, and Mn, composite oxides with lithium, and inorganic compounds such as transition metal sulfides. Specifically, 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. 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. In addition, conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. Moreover, you may mix and use said inorganic compound and organic compound.
リチウムイオン二次電池用の負極活物質としては、リチウムイオンをドーピングまたはインターカレーション可能なものであれば特に限定されない。例えば、金属Li、その合金であるスズ合金、シリコン合金、鉛合金等の合金系、ＬｉXＦｅ2Ｏ3、ＬｉXＦｅ3Ｏ4、ＬｉXＷＯ2、チタン酸リチウム、バナジウム酸リチウム、ケイ素酸リチウム等の金属酸化物系、ポリアセチレン、ポリ−ｐ−フェニレン等の導電性高分子系、ソフトカーボンやハードカーボンといった、アモルファス系炭素質材料や、高黒鉛化炭素材料等の人造黒鉛、あるいは天然黒鉛等の炭素質粉末、カーボンブラック、メソフェーズカーボンブラック、樹脂焼成炭素材料、気層成長炭素繊維、炭素繊維などの炭素系材料が挙げられる。これら負極活物質は、１種または複数を組み合わせて使用することもできる。 The negative electrode active material for the lithium ion secondary battery is not particularly limited as long as it can be doped or intercalated with lithium ions. For example, metal Li, alloys thereof such as tin alloys, silicon alloys, lead alloys, Li x Fe 2 O 3 , Li x Fe 3 O 4 , Li x WO 2 , lithium titanate, lithium vanadate, silicon Metal oxides such as lithium oxide, 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, or natural Examples thereof include carbonaceous powders such as graphite, carbon black, mesophase carbon black, resin-fired carbon materials, air-growth carbon fibers, and carbon fibers. These negative electrode active materials can be used alone or in combination.
これら活物質は、平均粒径が０．０５〜１００μｍの範囲内であることが好ましく、さらに好ましくは、０．１〜５０μｍの範囲内である。本明細書でいう活物質の平均粒径とは、活物質を電子顕微鏡で測定した粒子径の平均値である。 These active materials preferably have an average particle diameter in the range of 0.05 to 100 μm, and more preferably in the range of 0.1 to 50 μm. The average particle diameter of the active material as used herein is an average value of particle diameters obtained by measuring the active material with an electron microscope.
本発明では、上記課題に支障を及ぼさない範囲で、塗膜物性等の調整等の目的で、従来公知の分散剤や樹脂、添加剤等を併用しても良い。
そのような分散剤としては、例えば、ポリビニルブチラール樹脂やポリビニルピロリドン樹脂、従来公知の色素誘導体、低分子量の界面活性剤等が挙げられる。また樹脂としては、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン、ポリエチレン、ポリプロピレン、ポリメタクリル酸メチル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢酸ビニル、ポリアクリル酸、ポリアクリルアミド、ポリウレタン、ポリジメチルシロキサン、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、フェノール樹脂、スチレンブタジエンゴムなどの各種ゴム、リグニン、ペクチン、ゼラチン、キサンタンガム、ウェランガム、サクシノグリカン、セルロース系樹脂、ポリアルキレンオキサイド、ポリビニルエーテル、キチン類、キトサン類、デンプン等が挙げられる。また添加剤としては、リン化合物、硫黄化合物、有機酸、アミン化合物やアミド化合物、有機エステル、各種シラン系やチタン系、アルミニウム系のカップリング剤等が挙げられる。これらの従来公知の分散剤や樹脂、添加剤等は、単独または２種類以上併用して用いることが出来る。
In the present invention, conventionally known dispersants, resins, additives and the like may be used in combination for the purpose of adjusting the physical properties of the coating film and the like as long as the above-described problems are not affected.
Examples of such a dispersant include polyvinyl butyral resins and polyvinyl pyrrolidone resins, conventionally known pigment derivatives, low molecular weight surfactants, and the like. Examples of the resin include polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, polyacrylamide, and polyurethane. , Polydimethylsiloxane, epoxy resin, acrylic resin, polyester resin, melamine resin, phenol resin, styrene butadiene rubber and other rubbers, lignin, pectin, gelatin, xanthan gum, welan gum, succinoglycan, cellulosic resin, polyalkylene oxide, Examples include polyvinyl ether, chitins, chitosans, starch and the like. Examples of the additive include phosphorus compounds, sulfur compounds, organic acids, amine compounds and amide compounds, organic esters, various silane-based, titanium-based, and aluminum-based coupling agents. These conventionally known dispersants, resins, additives and the like can be used alone or in combination of two or more.
＜カーボンブラック分散液の用途＞
本発明のカーボンブラック分散液の利用分野としては、特に制限はないが、遮光性、導電性、耐久性、漆黒性等が要求される分野、例えば、グラビアインキ、オフセットインキ、磁気記録媒体用バックコート、静電トナー、インクジェット、自動車塗料、繊維・プラスチック形成材料、電池用電極、電子写真用シームレスベルトにおいて、安定かつ均一な組成物を提供し得るものである。中でも、ＮＭＰを使用すること、ポリフッ化ビニリデンやポリイミド前駆体などと相溶すること、および形成される塗膜や成型物の強度、柔軟性が良好なことから、リチウムイオン二次電池用電極、電気二重層キャパシタ用電極、リチウムイオンキャパシタ用電極、電子写真用シームレスベルトに好適などに用いられる。
<Uses of carbon black dispersion>
The field of application of the carbon black dispersion of the present invention is not particularly limited, but is a field where light shielding properties, electrical conductivity, durability, jetness, etc. are required, for example, gravure ink, offset ink, magnetic recording medium back In coatings, electrostatic toners, ink jets, automobile paints, fiber / plastic forming materials, battery electrodes, and electrophotographic seamless belts, a stable and uniform composition can be provided. Among them, the use of NMP, compatibility with polyvinylidene fluoride, polyimide precursors, and the like, and the strength and flexibility of the formed coating film and molded product, the electrode for lithium ion secondary battery, It is suitably used for electrodes for electric double layer capacitors, electrodes for lithium ion capacitors, and seamless belts for electrophotography.
本発明のカーボンブラック分散液を用いて、更にはポリフッ化ビニリデン、ポリテトラフルオロエチレン等のバインダーを添加してリチウムイオン二次電池用電極や電気二重層キャパシタ用電極、リチウムイオンキャパシタ用電極のプライマー層、更にコバルト酸リチウム、マンガン酸リチウム等のリチウム遷移金属複合酸化物、黒鉛、活性炭、グラファイト、カーボンナノチューブやカーボンナノファイバーなどの正極活物質や負極活物質を添加してリチウムイオン二次電池用電極や電気二重層キャパシタ用電極、リチウムイオンキャパシタ用電極の電極層を製造することができる。また、電子写真用シームレスベルトは、導電材としての本発明のカーボンブラック分散液、ポリイミド、ポリアミドイミド等およびその前駆体を成分として用いて、従来公知の方法などの公知の方法によって製造することができる。 Using the carbon black dispersion of the present invention and further adding a binder such as polyvinylidene fluoride and polytetrafluoroethylene, a primer for a lithium ion secondary battery electrode, an electric double layer capacitor electrode, or a lithium ion capacitor electrode Lithium ion secondary battery by adding a layer, and positive and negative active materials such as lithium transition metal composite oxides such as lithium cobaltate and lithium manganate, graphite, activated carbon, graphite, carbon nanotubes and carbon nanofibers Electrode layers for electrodes, electrodes for electric double layer capacitors, and electrodes for lithium ion capacitors can be manufactured. In addition, the electrophotographic seamless belt can be produced by a known method such as a conventionally known method using the carbon black dispersion of the present invention as a conductive material, polyimide, polyamideimide, etc. and its precursor as components. it can.
以下、実施例に基づき、本発明を詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。本実施例中、部は重量部を、％は重量％を、それぞれ表す。
実施例及び比較例で使用したカーボンブラック（「ＣＢ」と略記することがある）、ポリビニルアルコール樹脂（「ＰＶＡ」と略記することがある）、バインダー、電極活物質等を以下に示す。また、各表には、各原料の組成のみを記載しているが、特に記載の無い残りの成分は、全てＮ−メチル−２−ピロリドン（ＮＭＰ）である。
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example, unless the summary is exceeded. In this example, “part” represents “part by weight” and “%” represents “% by weight”.
Carbon black (sometimes abbreviated as “CB”), polyvinyl alcohol resin (sometimes abbreviated as “PVA”), binder, electrode active material, and the like used in Examples and Comparative Examples are shown below. Moreover, although only the composition of each raw material is described in each table, the remaining components not particularly described are all N-methyl-2-pyrrolidone (NMP).
＜カーボンブラック＞
・＃３０（三菱化学社製）：ファーネスブラック、平均一次粒子径３０ｎｍ、比表面積７４ｍ2／ｇ、以下＃３０と略記する。
・＃５（三菱化学社製）：ファーネスブラック、平均一次粒子径７６ｎｍ、比表面積２９ｍ2／ｇ、以下＃５と略記する。
・ＭＡ７７（三菱化学社製）：酸化処理カーボンブラック、平均一次粒子径２３ｎｍ、比表面積１３０ｍ2／ｇ、以下ＭＡ７７と略記する。
・デンカブラックＨＳ−１００（電気化学工業社製）：アセチレンブラック、平均一次粒子径４８ｎｍ、比表面積３９ｍ2／ｇ、以下ＨＳ−１００と略記する。
・デンカブラック粒状品（電気化学工業社製）：アセチレンブラック、平均一次粒子径３５ｎｍ、比表面積６９ｍ2／ｇ、以下粒状品と略記する。
・ＥＣ−３００Ｊ（アクゾ社製）：ケッチェンブラック、平均一次粒子径４０ｎｍ、比表面積８００ｍ2／ｇ、以下３００Ｊと略記する。
<Carbon black>
# 30 (Mitsubishi Chemical Co., Ltd.): Furnace black, average primary particle size 30 nm, specific surface area 74 m 2 / g, hereinafter abbreviated as # 30.
# 5 (Mitsubishi Chemical Co., Ltd.): Furnace black, average primary particle diameter 76 nm, specific surface area 29 m 2 / g, hereinafter abbreviated as # 5.
MA77 (Mitsubishi Chemical Corporation): oxidized carbon black, average primary particle size 23 nm, specific surface area 130 m 2 / g, hereinafter abbreviated as MA77.
Denka black HS-100 (manufactured by Denki Kagaku Kogyo): acetylene black, average primary particle size 48 nm, specific surface area 39 m 2 / g, hereinafter abbreviated as HS-100.
Denka black granular product (manufactured by Denki Kagaku Kogyo Co., Ltd.): Acetylene black, average primary particle size 35 nm, specific surface area 69 m 2 / g, hereinafter abbreviated as granular product.
EC-300J (manufactured by Akzo): Ketjen black, average primary particle size 40 nm, specific surface area 800 m 2 / g, hereinafter abbreviated as 300 J.
（カーボンブラックの平均一次粒子径の測定方法）
カーボンブラックの平均一次粒子径（ＭＶ）は、以下に示す方法により測定（算出）した。カーボンブラックの粉末にプロピレングリコールモノメチルエーテルアセテートを加え、樹脂型分散剤としてＤｉｓｐｅｒｂｙｋ−１６１を少量添加し、超音波洗浄機の水浴中で１分間分散処理して測定用試料を調製した。この試料を測定用ターゲットに塗布、乾燥し、透過型電子顕微鏡（日立ハイテクノロジーズ社製透過型電子顕微鏡Ｈ−７６５０）により、１００個以上のカーボンブラックの一次粒子が観察出来る写真を撮影した。撮影された画像にて、カーボンブラック粒子の任意の１００個を選び、その一次粒子の短軸径と長軸径の平均値を粒子径（ｄ）とし、次いで個々のカーボンブラックを、求めた粒子径（ｄ）を有する球とみなして、それぞれの粒子の体積（Ｖ）を求め、この作業を１００個のカーボンブラック粒子について行い、そこから下記式（１）を用いて算出した。
式（１） ＭＶ＝Σ（Ｖ・ｄ）／Σ（Ｖ）
(Measurement method of average primary particle size of carbon black)
The average primary particle size (MV) of carbon black was measured (calculated) by the method shown below. A sample for measurement was prepared by adding propylene glycol monomethyl ether acetate to a carbon black powder, adding a small amount of Disperbyk-161 as a resin-type dispersant, and dispersing the mixture in a water bath of an ultrasonic cleaner for 1 minute. This sample was applied to a measurement target, dried, and taken with a transmission electron microscope (transmission electron microscope H-7650, manufactured by Hitachi High-Technologies Corporation) to photograph 100 or more primary particles of carbon black. In the photographed image, an arbitrary 100 carbon black particles are selected, the average value of the minor axis diameter and major axis diameter of the primary particles is defined as the particle diameter (d), and then the individual carbon blacks are obtained. Considering it as a sphere having a diameter (d), the volume (V) of each particle was determined, and this operation was performed on 100 carbon black particles, and the calculation was performed using the following equation (1).
Formula (1) MV = Σ (V · d) / Σ (V)
＜ポリビニルアルコール樹脂＞
・クラレポバール Ｌ−８（クラレ社製）：ポリビニルアルコール樹脂、けん化度７１ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度５．５ｍＰａ・ｓ、以下Ｌ−８と略記する。
・クラレポバール Ｌ−１０（クラレ社製）：ポリビニルアルコール樹脂、けん化度７２ｍｏｌ％、平均重合度１０００以下、以下Ｌ−１０と略記する。
・クラレポバール Ｃ−５０６（クラレ社製）：カチオン変性ポリビニルアルコール樹脂、けん化度７６ｍｏｌ％、平均重合度６００、４％水溶液粘度５．１ｍＰａ・ｓ、以下Ｃ−５０６と略記する。
・クラレポバール ＫＬ−５０６（クラレ社製）：アニオン変性ポリビニルアルコール樹脂、けん化度７７ｍｏｌ％、平均重合度６００、４％水溶液粘度５．６ｍＰａ・ｓ、以下ＫＬ−５０６と略記する。
・ゴーセノール ＫＬ−０５（日本合成化学工業社製）：ポリビニルアルコール樹脂、けん化度８２ｍｏｌ％、以下、平均重合度１０００以下、４％水溶液粘度４．４ｍＰａ・ｓ、ＫＬ−０５と略記する。
・クラレポバール ＰＶＡ−２０５（クラレ社製）： ポリビニルアルコール樹脂、けん化度８８ｍｏｌ％、以下、平均重合度５００、４％水溶液粘度５．０ｍＰａ・ｓ、ＰＶＡ−２０５と略記する。
・ゴーセファイマー ＬＬ−０２（日本合成化学工業社製）：ポリビニルアルコール樹脂、けん化度５０ｍｏｌ％、平均重合度１０００以下、４％水溶液粘度７．７ｍＰａ・ｓ、以下、ＬＬ−０２と略記する。
・合成品１：ポリビニルアルコール樹脂、けん化度６０ｍｏｌ％、平均重合度約５００、４％水溶液粘度５．２ｍＰａ・ｓ。
・合成品２：ポリビニルアルコール樹脂、けん化度８５ｍｏｌ％、平均重合度約５００、４％水溶液粘度５．７ｍＰａ・ｓ。
・合成品３：ポリビニルアルコール樹脂、けん化度７２ｍｏｌ％、平均重合度約１００、４％水溶液粘度２．０ｍＰａ・ｓ。
・合成品４：ポリビニルアルコール樹脂、けん化度７０ｍｏｌ％、平均重合度約１５００、４％水溶液粘度１９．８ｍＰａ・ｓ。
尚、上記合成品１、合成品２、合成品３、合成品４は、業界公知の方法により、ポリ酢酸ビニルを水酸化ナトリウムでけん化することで得たものである。
<Polyvinyl alcohol resin>
Kuraray Poval L-8 (manufactured by Kuraray Co., Ltd.): polyvinyl alcohol resin, saponification degree 71 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 5.5 mPa · s, hereinafter abbreviated as L-8.
Kuraray Poval L-10 (manufactured by Kuraray): polyvinyl alcohol resin, saponification degree 72 mol%, average polymerization degree 1000 or less, hereinafter abbreviated as L-10.
Kuraray Poval C-506 (manufactured by Kuraray): cation-modified polyvinyl alcohol resin, saponification degree 76 mol%, average polymerization degree 600, 4% aqueous solution viscosity 5.1 mPa · s, hereinafter abbreviated as C-506.
Kuraray Poval KL-506 (manufactured by Kuraray Co., Ltd.): anion-modified polyvinyl alcohol resin, saponification degree 77 mol%, average polymerization degree 600, 4% aqueous solution viscosity 5.6 mPa · s, hereinafter abbreviated as KL-506.
Gohsenol KL-05 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.): polyvinyl alcohol resin, saponification degree 82 mol%, hereinafter, average polymerization degree 1000 or less, 4% aqueous solution viscosity 4.4 mPa · s, abbreviated as KL-05.
Kuraray Poval PVA-205 (manufactured by Kuraray Co., Ltd.): Polyvinyl alcohol resin, saponification degree 88 mol%, hereinafter, average polymerization degree 500, 4% aqueous solution viscosity 5.0 mPa · s, abbreviated as PVA-205.
Goosephimer LL-02 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.): polyvinyl alcohol resin, saponification degree 50 mol%, average polymerization degree 1000 or less, 4% aqueous solution viscosity 7.7 mPa · s, hereinafter abbreviated as LL-02.
Synthetic product 1: polyvinyl alcohol resin, saponification degree 60 mol%, average polymerization degree about 500, 4% aqueous solution viscosity 5.2 mPa · s.
Synthetic product 2: Polyvinyl alcohol resin, saponification degree 85 mol%, average polymerization degree about 500, 4% aqueous solution viscosity 5.7 mPa · s.
Synthetic product 3: polyvinyl alcohol resin, saponification degree 72 mol%, average degree of polymerization about 100, 4% aqueous solution viscosity 2.0 mPa · s.
Synthetic product 4: polyvinyl alcohol resin, saponification degree 70 mol%, average polymerization degree about 1500, 4% aqueous solution viscosity 19.8 mPa · s.
The synthetic product 1, the synthetic product 2, the synthetic product 3, and the synthetic product 4 are obtained by saponifying polyvinyl acetate with sodium hydroxide by a method known in the industry.
＜バインダー＞
・ＫＦポリマーＷ１１００（クレハ社製）：ポリフッ化ビニリデン（ＰＶＤＦ）、以下、ＰＶＤＦと略記する。
・ＫＦポリマーＷ７３００（クレハ社製）：ポリフッ化ビニリデン（ＰＶＤＦ）、以下、＃７３００と略記する。
<Binder>
KF polymer W1100 (manufactured by Kureha): polyvinylidene fluoride (PVDF), hereinafter abbreviated as PVDF.
-KF polymer W7300 (manufactured by Kureha): polyvinylidene fluoride (PVDF), hereinafter abbreviated as # 7300.
＜活物質＞
・ＨＬＣ−２２（本荘ケミカル社製）：正極活物質コバルト酸リチウム（ＬｉＣｏＯ2）、平均粒径６．６μｍ、比表面積０．６２ｍ2／ｇ、以下、ＬＣＯと略記する。
・ＭＣＭＢ６−２８（大阪ガスケミカル社製）：負極活物質メソフェーズカーボン（ＭＦＣ）、平均粒径５〜７μｍ、比表面積４ｍ2／ｇ、以下、ＭＦＣと略記する。
<Active material>
HLC-22 (Honjo Chemical Co., Ltd.): positive electrode active material lithium cobaltate (LiCoO 2 ), average particle size 6.6 μm, specific surface area 0.62 m 2 / g, hereinafter abbreviated as LCO.
MCMB6-28 (manufactured by Osaka Gas Chemical Company): negative electrode active material mesophase carbon (MFC), average particle size 5 to 7 μm, specific surface area 4 m 2 / g, hereinafter abbreviated as MFC.
＜カーボンブラック分散液の評価＞
実施例、比較例で得られたカーボンブラック分散液の評価は、粘度、分散後平均粒径を測定することにより行った。
<Evaluation of carbon black dispersion>
The carbon black dispersions obtained in Examples and Comparative Examples were evaluated by measuring the viscosity and average particle diameter after dispersion.
粘度値の測定は、Ｂ型粘度計（東機産業社製「ＢＬ」）を用いて、分散液温度２５℃、Ｂ型粘度計ローター回転速度６０ｒｐｍにて、分散液をヘラで充分に撹拌した後、直ちに行った。測定に使用したローターは、粘度値が１００ｍＰａ・ｓ未満の場合はＮｏ．１を、１００以上５００ｍＰａ・ｓ未満の場合はＮｏ．２を、５００以上２０００ｍＰａ・ｓ未満の場合はＮｏ．３を、２０００以上１００００ｍＰａ・ｓ未満の場合はＮｏ．４のものをそれぞれ用いた。得られた粘度値が１００００ｍＰａ・ｓ以上の場合については、「＞１００００」と記載したが、これは評価に用いたＢ型粘度計では評価不可能なほどに高粘度であったことを表す。低粘度であるほど分散性が良好であり、高粘度であるほど分散性が不良である。貯蔵安定性の評価は、カーボンブラック分散液を５０℃にて、３０日間静置して保存した後の、粘度値の変化から評価した。変化の少ないものほど安定性が良好であることを示す。 The viscosity value was measured using a B-type viscometer (“BL” manufactured by Toki Sangyo Co., Ltd.), and the dispersion was sufficiently stirred with a spatula at a dispersion temperature of 25 ° C. and a B-type viscometer rotor rotation speed of 60 rpm. Then went immediately. The rotor used for the measurement is No. when the viscosity value is less than 100 mPa · s. No. 1 is 100 or more and less than 500 mPa · s. 2 is 500 or more and less than 2000 mPa · s. 3 is 2000 or more and less than 10,000 mPa · s. Four of each were used. The case where the obtained viscosity value was 10,000 mPa · s or more was described as “> 10000”, but this indicates that the viscosity was so high that it could not be evaluated with the B-type viscometer used for the evaluation. The lower the viscosity, the better the dispersibility, and the higher the viscosity, the poor the dispersibility. The storage stability was evaluated from the change in viscosity value after the carbon black dispersion was stored at 50 ° C. for 30 days. The smaller the change, the better the stability.
また、分散後平均粒径の測定は、カーボンブラック分散液をＮＭＰにより適切な濃度に希釈した後に、超音波処理を施した液を測定サンプルとして用い、動的光散乱法方式の粒度分布計（日機装社製「ナノトラックＵＰＡ−ＥＸ」、光源波長７８０ｎｍ）を用いて平均粒径（Ｄ５０値）を測定することにより行った。各種測定条件は、上記方法によりＮＭＰ希釈した分散液のローディングインデックス値を０．７以上１．３以下に、粒子条件を、吸収性粒子、粒子形状非球形、密度１．８０とし、溶媒条件を、溶媒屈折率１．４７、液温２０℃における溶媒粘度１．８０ｍＰａ・ｓ、液温２５℃における溶媒粘度１．６５ｍＰａ・ｓと設定し、得られたメジアン径をＤ５０値として表記した。測定結果は、液温２５℃のＮＭＰ溶剤についてバックグラウンド値を測定した後、上記方法にて調製した液温２５℃のサンプルを測定容器に充填し、上記測定条件にて測定を行うことにより得た。
同じカーボンブラックを使用した場合、Ｄ５０値が小さいほど分散性が良好であり、大きいほど分散性が不良であることを示す。貯蔵安定性の評価は、カーボンブラック分散液を５０℃にて、３０日間静置して保存した後のＤ５０値の変化から評価した。変化の少ないものほど安定性が良好であることを示す。
In addition, the average particle size after dispersion was measured by diluting the carbon black dispersion with NMP to an appropriate concentration and then using the ultrasonically treated liquid as a measurement sample, and using a dynamic light scattering particle size distribution analyzer ( The measurement was performed by measuring the average particle diameter (D50 value) using “Nanotrack UPA-EX” manufactured by Nikkiso Co., Ltd., light source wavelength 780 nm). Various measurement conditions were such that the loading index value of the dispersion diluted with NMP by the above method was 0.7 or more and 1.3 or less, the particle conditions were absorbent particles, particle shape non-spherical, density 1.80, and the solvent conditions were The solvent refractive index was 1.47, the solvent viscosity was 1.80 mPa · s at a liquid temperature of 20 ° C., the solvent viscosity was 1.65 mPa · s at a liquid temperature of 25 ° C., and the obtained median diameter was expressed as a D50 value. The measurement result is obtained by measuring the background value of the NMP solvent at a liquid temperature of 25 ° C., filling a sample with the liquid temperature of 25 ° C. prepared by the above method into a measurement container, and performing the measurement under the above measurement conditions. It was.
When the same carbon black is used, the smaller the D50 value, the better the dispersibility, and the larger the D50 value, the poorer the dispersibility. The storage stability was evaluated from the change in D50 value after storing the carbon black dispersion at 50 ° C. for 30 days. The smaller the change, the better the stability.
＜カーボンブラック分散液の調製＞
（けん化度の異なるポリビニルアルコール樹脂を用いたカーボンブラック分散液）
［実施例１−１〜実施例１−７］
表１に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコール樹脂を仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで２時間分散し、各カーボンブラック分散液を得た。いずれも低粘度かつＤ５０値が小さく、貯蔵安定性も良好であった。また、ポリビニルアルコール樹脂の変性の有無は、分散剤としての性能には大きな影響を与えないことが明らかとなった。
<Preparation of carbon black dispersion>
(Carbon black dispersion using polyvinyl alcohol resins with different degrees of saponification)
[Example 1-1 to Example 1-7]
In accordance with the composition shown in Table 1, NMP and various polyvinyl alcohol resins are charged into a glass bottle, mixed and dissolved or mixed and dispersed, then various carbon blacks are added, and 1.25 mmφ zirconia beads are used as media and dispersed for 2 hours using a paint shaker. Each carbon black dispersion was obtained. In all cases, the viscosity was low, the D50 value was small, and the storage stability was good. Moreover, it became clear that the presence or absence of modification | denaturation of polyvinyl alcohol resin does not have big influence on the performance as a dispersing agent.
［比較例１−１〜比較例１−２］
表１に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコール樹脂とを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで２時間分散した。しかし、得られた分散液は、いずれも著しく高粘度な状態であり、Ｄ５０値が大きいことから、カーボンブラックを十分に分散する事が出来ていないことがわかる。この結果から、カーボンブラックの比表面積に対するポリビニルアルコール樹脂の添加量より算出されるａ値が、０．０００１７≦ａ≦０．００２５６の範囲内であっても、けん化度が６０ｍｏｌ％未満または８５ｍｏｌ％を越えるポリビニルアルコール樹脂を使用した場合には、所望とする高濃度かつ低粘度のカーボンブラック分散液を得る事ができないことが明らかとなった。
[Comparative Example 1-1 to Comparative Example 1-2]
In accordance with the composition shown in Table 1, NMP and various polyvinyl alcohol resins were charged into a glass bottle, mixed and dissolved or mixed and dispersed, then various carbon blacks were added, and 1.25 mmφ zirconia beads were used as media for 2 hours with a paint shaker. Distributed. However, all of the obtained dispersions are in a very high viscosity state and have a large D50 value, which indicates that carbon black cannot be sufficiently dispersed. From this result, even if the a value calculated from the addition amount of the polyvinyl alcohol resin with respect to the specific surface area of carbon black is within the range of 0.00017 ≦ a ≦ 0.00256, the degree of saponification is less than 60 mol% or 85 mol%. It has been clarified that when a polyvinyl alcohol resin exceeding the above range is used, a desired high concentration and low viscosity carbon black dispersion cannot be obtained.
（種類の異なるカーボンブラックとポリビニルアルコール樹脂含有量の異なるカーボンブラック分散液）
［実施例１−８〜実施例１−２４］
表１に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコール樹脂を仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで２時間分散し、各カーボンブラック分散液を得た。いずれも低粘度かつＤ５０値が小さく、貯蔵安定性も良好であった。
(Carbon black dispersions with different types of carbon black and polyvinyl alcohol resin content)
[Example 1-8 to Example 1-24]
In accordance with the composition shown in Table 1, NMP and polyvinyl alcohol resin are charged into a glass bottle and mixed and dissolved or mixed and dispersed. Then, various carbon blacks are added and dispersed in a paint shaker for 2 hours using 1.25 mmφ zirconia beads as media. Each carbon black dispersion was obtained. In all cases, the viscosity was low, the D50 value was small, and the storage stability was good.
［比較例１−３、参考例１−１］
表１に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコール樹脂を仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、１．２５ｍｍφジルコニアビーズをメディアとして、ペイントシェーカーで２時間分散し、各カーボンブラック分散液を得た。得られた分散液は、いずれも著しく高粘度な状態であり、Ｄ５０値が大きいことから、カーボンブラックを十分に分散する事が出来ていない状態であった。この結果から、けん化度が６０〜８５ｍｏｌ％のポリビニルアルコール樹脂を使用しても、カーボンブラックの比表面積に対するポリビニルアルコール樹脂の添加量より算出されるａ値が、０．０００１７≦ａ≦０．００２５６の範囲以外の場合には、所望とする高濃度かつ低粘度のカーボンブラック分散液を得る事ができないことが明らかとなった。
[Comparative Example 1-3, Reference Example 1-1]
In accordance with the composition shown in Table 1, NMP and polyvinyl alcohol resin are charged into a glass bottle and mixed and dissolved or mixed and dispersed. Then, various carbon blacks are added and dispersed in a paint shaker for 2 hours using 1.25 mmφ zirconia beads as media. Each carbon black dispersion was obtained. All of the obtained dispersions were in a state of extremely high viscosity and the D50 value was large, so that carbon black could not be sufficiently dispersed. From this result, even when a polyvinyl alcohol resin having a saponification degree of 60 to 85 mol% is used, the a value calculated from the addition amount of the polyvinyl alcohol resin with respect to the specific surface area of carbon black is 0.00017 ≦ a ≦ 0.00256. In other cases, it became clear that a desired high concentration and low viscosity carbon black dispersion could not be obtained.
＜バインダーを含むカーボンブラック分散液の調製＞
［実施例２−１〜実施例２−１６］
表２に示す組成に従い、ガラス瓶にＮＭＰと各種ポリビニルアルコール樹脂と各種バインダーを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。
<Preparation of carbon black dispersion containing binder>
[Example 2-1 to Example 2-16]
In accordance with the composition shown in Table 2, NMP, various polyvinyl alcohol resins and various binders are charged into a glass bottle, and after thoroughly mixing, dissolving or mixing, various carbon blacks are added and dispersed with a homogenizer for 1 hour. Got. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［実施例２−１７］
表２に示す組成に従い、ガラス瓶にＮＭＰとポリビニルアルコール樹脂を仕込み、充分に混合溶解した。次いで、カーボンブラックとＰＶＤＦとを均質に混合した粉体混合品を調製し、これを事前に調製したポリビニルアルコールのＮＭＰ溶液に添加した。その後、ホモジナイザーで１時間分散し、カーボンブラック分散液を得た。粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。
[Example 2-17]
In accordance with the composition shown in Table 2, NMP and polyvinyl alcohol resin were charged into a glass bottle and sufficiently mixed and dissolved. Next, a powder mixture in which carbon black and PVDF were homogeneously mixed was prepared, and this was added to an NMP solution of polyvinyl alcohol prepared in advance. Then, it disperse | distributed for 1 hour with the homogenizer, and obtained the carbon black dispersion liquid. There were no coarse particles, the viscosity was low, and the storage stability was good.
［実施例２−１８］
表２に示す組成に従い、ガラス瓶に実施例１−２のカーボンブラック分散液を６０部、ＰＶＤＦを６部、ＮＭＰを３４部加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。いずれも粗大粒子がなく、かつ低粘度であり、貯蔵安定性も良好であった。
[Example 2-18]
According to the composition shown in Table 2, 60 parts of the carbon black dispersion liquid of Example 1-2, 6 parts of PVDF, and 34 parts of NMP were added to a glass bottle and dispersed with a homogenizer for 1 hour to obtain each carbon black dispersion liquid. All of them had no coarse particles, had a low viscosity, and had good storage stability.
［比較例２−１〜比較例２−５］
表２に示す組成に従い、ガラス瓶にＮＭＰと、各種ポリビニルアルコール樹脂とＰＶＤＦを仕込み、充分に混合溶解、または混合分散した後、各種カーボンブラックを加え、ホモジナイザーで１時間分散し、各カーボンブラック分散液を得た。しかし、得られた分散液の粘度は、バインダーを添加せずに調製した場合と同様に高粘度であり、カーボンブラックおよびバインダー濃度のさらなる向上はできないことが明らかとなった。
[Comparative Examples 2-1 to 2-5]
In accordance with the composition shown in Table 2, NMP, various polyvinyl alcohol resins and PVDF are charged into a glass bottle, and after thoroughly mixing, dissolving or mixing, various carbon blacks are added and dispersed for 1 hour with a homogenizer. Got. However, it was revealed that the viscosity of the obtained dispersion was as high as that prepared without adding a binder, and the carbon black and binder concentrations could not be further improved.
表２より、ＮＭＰに溶解、または分散可能な樹脂をバインダーとして用いた場合、得られるカーボンブラック分散液の性状は、表１のバインダーを添加せずに分散液を調製した場合と同様に、高濃度かつ低粘度であり、貯蔵安定性も良好な分散液を得られることが分かる。 From Table 2, when a resin that can be dissolved or dispersed in NMP is used as a binder, the properties of the resulting carbon black dispersion are as high as when the dispersion was prepared without adding the binder of Table 1. It can be seen that a dispersion having a low concentration and low viscosity and good storage stability can be obtained.
＜正極活物質または負極活物質を含むカーボンブラック分散液の調製＞
［実施例３−１〜実施例３−３、実施例３−５〜実施例３−１４］
表３に示す組成に従い、実施例２−１〜実施例２−３および実施例２−５〜実施例２−１４で得たバインダーを含有するカーボンブラック分散液に対し、正極活物質であるＬＣＯを仕込み、ディスパーにより充分に混合し、各混合液を得た。用いたカーボンブラック分散液が低粘度であるために、ＬＣＯを多量に添加することができ、また、得られた混合液も低粘度な状態であった。
<Preparation of carbon black dispersion containing positive electrode active material or negative electrode active material>
[Example 3-1 to Example 3-3, Example 3-5 to Example 3-14]
According to the composition shown in Table 3, LCO, which is a positive electrode active material, with respect to the carbon black dispersion containing the binder obtained in Example 2-1 to Example 2-3 and Example 2-5 to Example 2-14 Were mixed well with a disper to obtain each mixture. Since the carbon black dispersion used had a low viscosity, a large amount of LCO could be added, and the resulting mixture was also in a low viscosity state.
［実施例３−４］
粒状品を２．６７部、ＰＶＤＦを１．３３部、Ｌ−８を０．１３部、ＬＣＯを６２．７部を均質に混合した粉体混合品を調製後、ＮＭＰ３３．１７部に対して粉体混合品全量の半分を添加し、プラネタリーミキサーにて３０分間処理を行った。次いで、残った粉体混合品の半分を添加してプラネタリーミキサーにて３０分間処理し、その後、残った粉体混合品を全て添加してプラネタリーミキサーにて１時間処理することにより、正極活物質であるＬＣＯを含有したカーボンブラック分散液を得た。得られた液は、実施例３−２の場合と同様、低粘度な状態であった。
[Example 3-4]
After preparing a powder mixture in which 2.67 parts of granular product, 1.33 parts of PVDF, 0.13 part of L-8, and 62.7 parts of LCO were homogeneously mixed, 33.17 parts of NMP Half of the total amount of the powder mixture was added and treated for 30 minutes with a planetary mixer. Next, half of the remaining powder mixture was added and treated with a planetary mixer for 30 minutes, and then all the remaining powder mixture was added and treated with a planetary mixer for 1 hour. A carbon black dispersion containing LCO as an active material was obtained. The obtained liquid was in a low viscosity state as in Example 3-2.
［実施例３−１５〜実施例３−１８］
表３に示す組成に従い、実施例２−１〜実施例２−３および実施例２−９で得た、バインダーを含有するカーボンブラック分散液に対し、負極活物質であるＭＦＣを仕込み、ディスパーにより充分に混合し、各混合液を得た。用いたカーボンブラック分散液が低粘度であるために、ＭＦＣを多量に添加することができ、また、得られた混合液も低粘度な状態であった。
[Example 3-15 to Example 3-18]
In accordance with the composition shown in Table 3, MFC, which is a negative electrode active material, was charged into the carbon black dispersion containing the binder obtained in Example 2-1 to Example 2-3 and Example 2-9, and a disper was used. Mix well to obtain each mixture. Since the carbon black dispersion used had a low viscosity, a large amount of MFC could be added, and the resulting mixture was also in a low viscosity state.
［比較例３−１〜比較例３−３］
表３に示す組成に従い、比較例２−３〜比較例２−５で得た、バインダーを含有するカーボンブラック分散液に対し、正極活物質であるＬＣＯを仕込み、ディスパーにより充分に混合し、各混合液を得た。いずれも、用いたカーボンブラック分散液の粘度値が高いことから、実施例３−１〜実施例３−１４と比較して、ＬＣＯを添加した際の粘度値の上昇が大きく、また、安定性評価試験における粘度の上昇幅も大きかった。
[Comparative Examples 3-1 to 3-3]
In accordance with the composition shown in Table 3, the carbon black dispersion containing the binder obtained in Comparative Examples 2-3 to 2-5 was charged with LCO as the positive electrode active material, and thoroughly mixed with a disper. A mixture was obtained. In any case, since the viscosity value of the carbon black dispersion used was high, the increase in the viscosity value when LCO was added was larger than in Examples 3-1 to 3-14, and the stability was also high. The increase in viscosity in the evaluation test was also large.
［比較例３−４〜比較例３−６］
表３に示す組成に従い、比較例２−３〜比較例２−５で得た、バインダーを含有するカーボンブラック分散液に対し、負極活物質であるＭＦＣを仕込み、ディスパーにより充分に混合し、各混合液を得た。いずれも、用いたカーボンブラック分散液の粘度値が高いことから、実施例３−１５〜実施例３−１８と比較して、ＭＦＣを添加した際の粘度値の上昇が大きく、また、安定性評価試験における粘度の上昇幅も大きかった。
[Comparative Example 3-4 to Comparative Example 3-6]
In accordance with the composition shown in Table 3, MFC as the negative electrode active material was charged into the carbon black dispersion containing the binder obtained in Comparative Example 2-3 to Comparative Example 2-5, and thoroughly mixed with a disper. A mixture was obtained. In any case, since the viscosity value of the carbon black dispersion used is high, the increase in the viscosity value when MFC is added is larger than that in Examples 3-15 to 3-18, and the stability is high. The increase in viscosity in the evaluation test was also large.
＜電池電極合材層の作製＞
上記の各実施例、比較例で得られた正極活物質または負極活物質を含むカーボンブラック分散液を電池電極合材液として、ポリエチレンテレフタレート（ＰＥＴ）フィルム上にドクターブレードを用いて塗工した後、減圧下１２０℃で３０分間乾燥し、乾燥後膜厚１００μｍの塗膜（電池電極合材層）を作製した。
得られた電池電極合材層の評価は、表面抵抗と塗膜外観により行った。表面抵抗の測定にはロレスタ−ＧＰ（三菱化学アナリテック社製）を用い、ＪＩＳ Ｋ７１９４に準じて測定した。
表面抵抗は、数値の小さい程、良好であることを示す。また、塗膜外観は、目視で、○：問題なし（良好）、△：斑模様あり（不良）、×：粗粒の筋引きあり（極めて不良）、とした。
<Preparation of battery electrode composite layer>
After applying the carbon black dispersion containing the positive electrode active material or the negative electrode active material obtained in each of the above Examples and Comparative Examples as a battery electrode mixture liquid on a polyethylene terephthalate (PET) film using a doctor blade Then, the film was dried at 120 ° C. under reduced pressure for 30 minutes, and a coating film (battery electrode mixture layer) having a film thickness of 100 μm was produced after drying.
Evaluation of the obtained battery electrode mixture layer was performed by surface resistance and coating film appearance. The surface resistance was measured according to JIS K7194 using Loresta GP (manufactured by Mitsubishi Chemical Analytech).
The smaller the numerical value, the better the surface resistance. Further, the appearance of the coating film was visually evaluated as ◯: no problem (good), Δ: spotted pattern (bad), and x: coarse-grained stripes (very bad).
［実施例４−１〜実施例４−１１、比較例４−１〜比較例４−３］
正極合材液として、実施例３−１〜実施例３−３および実施例３−５〜実施例３−１２、比較例３−１〜比較例３−３で得た電池電極合材液を使用して、正極合材層（電池電極合材層）を作製した。評価結果を表４に示した。
[Example 4-1 to Example 4-11, Comparative Example 4-1 to Comparative Example 4-3]
As the positive electrode mixture liquid, the battery electrode mixture liquids obtained in Example 3-1 to Example 3-3, Example 3-5 to Example 3-12, and Comparative Example 3-1 to Comparative Example 3-3 were used. The positive electrode composite material layer (battery electrode composite material layer) was produced by using it. The evaluation results are shown in Table 4.
［実施例４−１２〜実施例４−１５、比較例４−４〜比較例４−５］
負極合材液としては、実施例３−１５〜実施例３−１８、比較例３−４〜比較例３−５で得た電池電極合材液を使用して、負極合材層（電池電極合材層）を作製した。評価結果を表４に示した。
表４より、実施例４−１〜実施例４−１５の電池電極合材層は、比較例４−１〜比較例４−５の電池電極合材層と比較して塗膜外観が良好であり、さらに、塗膜の表面抵抗が優れていることが明らかとなった。比較例４−１〜比較例４−５では、使用した電極合材液の粘度が高すぎるために塗工が困難であり、さらに、多量に含まれるポリビニルアルコール樹脂が絶縁成分として機能した結果、表面抵抗値が高くなったものと考えられる。
[Example 4-12 to Example 4-15, Comparative Example 4-4 to Comparative Example 4-5]
As the negative electrode mixture liquid, the battery electrode mixture liquid obtained in Examples 3-15 to 3-18 and Comparative Example 3-4 to Comparative Example 3-5 was used, and the negative electrode mixture layer (battery electrode) A composite layer) was prepared. The evaluation results are shown in Table 4.
From Table 4, the battery electrode mixture layer of Example 4-1 to Example 4-15 has a better coating film appearance than the battery electrode mixture layer of Comparative Example 4-1 to Comparative Example 4-5. Furthermore, it was revealed that the surface resistance of the coating film was excellent. In Comparative Example 4-1 to Comparative Example 4-5, coating is difficult because the viscosity of the electrode mixture solution used is too high, and the polyvinyl alcohol resin contained in a large amount functions as an insulating component. It is thought that the surface resistance value was increased.
＜リチウムイオン二次電池正極評価用セルの組み立て＞
［実施例５−１〜実施例５−１１、比較例５−１〜比較例５−３］
先に調製した電池電極合材液（実施例３−１〜実施例３−３および実施例３−５〜実施例３−１２、比較例３−１〜比較例３−３の正極合材液）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、減圧下１２０℃で加熱乾燥した後、ローラープレス機にて圧延処理し、厚さ１００μｍの正極合材層を作製した。これを直径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容量比１:１で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（宝泉社製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った。
<Assembly of lithium ion secondary battery positive electrode evaluation cell>
[Example 5-1 to Example 5-11, Comparative Example 5-1 to Comparative Example 5-3]
The previously prepared battery electrode mixture liquids (the positive electrode mixture liquids of Example 3-1 to Example 3-3 and Example 3-5 to Example 3-12, Comparative Example 3-1 to Comparative Example 3-3) ) Is applied onto a 20 μm thick aluminum foil as a current collector using a doctor blade, dried at 120 ° C. under reduced pressure, and then rolled with a roller press to obtain a positive electrode composite having a thickness of 100 μm. A material layer was prepared. This is a punching working electrode with a diameter of 9 mm, a metallic lithium foil (thickness 0.15 mm) as a counter electrode, and a separator made of a porous polypropylene film (# 2400 manufactured by Celgard) is inserted and laminated between the working electrode and the counter electrode, An electrolyte solution (nonaqueous electrolyte solution in which LiPF 6 is dissolved at a concentration of 1M in a mixed solvent of ethylene carbonate and diethyl carbonate mixed at a volume ratio of 1: 1) is filled and a bipolar electrode type metal cell (HS manufactured by Hosen Co., Ltd.) Flat cell). The cell was assembled in a glove box substituted with argon gas.
＜リチウムイオン二次電池負極評価用セルの組み立て＞
［実施例５−１２〜実施例５−１５、比較例５−４〜比較例５−５］
先に調製した電池電極合材液（実施例３−１５〜実施例３−１８、比較例３−４〜比較例３−５の負極合材液）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、減圧下１２０℃で加熱乾燥した後、ローラープレス機にて圧延処理し、厚さ１００μｍの負極合材層を作製した。これを直径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容量比１:１で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（宝泉社製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った。
<Assembly of lithium ion secondary battery negative electrode evaluation cell>
[Example 5-12 to Example 5-15, Comparative Example 5-4 to Comparative Example 5-5]
The previously prepared battery electrode mixture liquids (the negative electrode mixture liquids of Examples 3-15 to 3-18 and Comparative Examples 3-4 to 3-5) having a thickness of 20 μm serving as a current collector After apply | coating using a doctor blade on aluminum foil, after heat-drying at 120 degreeC under pressure reduction, it rolled by the roller press machine and produced the negative mix layer of thickness 100 micrometers. This is a punching working electrode with a diameter of 9 mm, a metallic lithium foil (thickness 0.15 mm) as a counter electrode, and a separator made of a porous polypropylene film (# 2400 manufactured by Celgard) is inserted and laminated between the working electrode and the counter electrode, An electrolyte solution (nonaqueous electrolyte solution in which LiPF 6 is dissolved at a concentration of 1M in a mixed solvent of ethylene carbonate and diethyl carbonate mixed at a volume ratio of 1: 1) is filled and a bipolar electrode type metal cell (HS manufactured by Hosen Co., Ltd.) Flat cell). The cell was assembled in a glove box substituted with argon gas.
＜リチウムイオン二次電池正極特性評価＞
作製した正極評価用セルを２５℃で、北斗電工社製ＳＭ−８を使用して、充電レート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５０サイクル行い、充放電を行った。評価後のセルを分解し、電極塗膜の外観（５０サイクル後の塗膜外観）を目視にて確認した。塗膜外観の評価基準は、剥がれが認められず外観に全く変化が無い場合を○（極めて良好）、剥がれてはいないが外観に変化が認められる場合を△（良好）、部分的に合材が集電体より剥がれが認められる場合を×（不良）とした。また、容量維持率は、数値が１００％に近いものほど良好であることを示す。評価結果を表５に示した。
<Characteristic evaluation of lithium ion secondary battery positive electrode>
The produced positive electrode evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 4.2 V) at a charge rate of 1.0 C using a Hokuto Denko SM-8 at 25 ° C. Charging / discharging for discharging to a discharge lower limit voltage of 3.0 V at a constant current at a rate was defined as one cycle (charging / discharging interval pause time 30 minutes), and this cycle was performed for a total of 50 cycles for charging / discharging. The cell after evaluation was disassembled, and the appearance of the electrode coating film (the coating film appearance after 50 cycles) was visually confirmed. Evaluation criteria for coating film appearance are ○ (very good) when no peeling is observed and no change in appearance, △ (good) when there is no peeling but change in appearance, partially mixed Was evaluated as x (defect) when peeling from the current collector was observed. Moreover, a capacity | capacitance maintenance factor shows that it is so favorable that a numerical value is near 100%. The evaluation results are shown in Table 5.
＜リチウムイオン二次電池負極特性評価＞
作製した負極評価用セルを２５℃で、北斗電工社製ＳＭ−８を使用して、充電レート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５０サイクル行い、充放電サイクルを行った。評価後のセルを分解し、電極塗膜の外観（５０サイクル後の塗膜外観）について、正極特性評価と同じ基準で評価した。評価結果を表５に示した。
<Evaluation of lithium ion secondary battery negative electrode characteristics>
The produced negative electrode evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 0.5 V) at a charge rate of 1.0 C using a Hokuto Denko SM-8 at 25 ° C. Charging / discharging for discharging until the voltage becomes 1.5 V at a constant current rate was set to one cycle (charging / discharging interval pause time 30 minutes), and this cycle was performed for a total of 50 cycles to perform a charging / discharging cycle. The cell after the evaluation was disassembled, and the appearance of the electrode coating film (the coating film appearance after 50 cycles) was evaluated based on the same criteria as the positive electrode characteristic evaluation. The evaluation results are shown in Table 5.
表５より、本発明の電極を使用した実施例５−１〜実施例５−１１および実施例５−１２〜実施例５−１５は、比較例５−１〜比較例５−３および比較例５−４〜比較例５−５と比較して、塗膜外観が良好であり、かつ、５０サイクル後の容量維持率についても、良好な結果であった。 From Table 5, Example 5-1 to Example 5-11 and Example 5-12 to Example 5-15 using the electrode of the present invention are Comparative Example 5-1 to Comparative Example 5-3 and Comparative Example. Compared with 5-4 to Comparative Example 5-5, the appearance of the coating film was good, and the capacity retention rate after 50 cycles was also good.
表５より、実施例５−１〜実施例５−１５は５０サイクルの充放電サイクル後も、塗膜外観が良好で、かつ容量維持率も良好であることが判明した。一方、比較例５−１〜比較例５−５は、良好な塗膜を得ることが出来なかったため、正極特性および負極特性を評価することが出来なかった。 From Table 5, it was found that Example 5-1 to Example 5-15 had a good coating film appearance and a good capacity retention rate even after 50 charge / discharge cycles. On the other hand, since Comparative Example 5-1 to Comparative Example 5-5 were unable to obtain a good coating film, the positive electrode characteristics and the negative electrode characteristics could not be evaluated.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013215953A JP6142418B2 (en) | 2013-02-27 | 2013-10-17 | Carbon black dispersion and use thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013036920 | 2013-02-27 | ||
| JP2013036920 | 2013-02-27 | ||
| JP2013215953A JP6142418B2 (en) | 2013-02-27 | 2013-10-17 | Carbon black dispersion and use thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013125306A Division JP5454725B1 (en) | 2013-02-27 | 2013-06-14 | Carbon black dispersion and use thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2014193996A true JP2014193996A (en) | 2014-10-09 |
| JP2014193996A5 JP2014193996A5 (en) | 2015-04-16 |
| JP6142418B2 JP6142418B2 (en) | 2017-06-07 |
Family
ID=50614572
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013125306A Active JP5454725B1 (en) | 2013-02-27 | 2013-06-14 | Carbon black dispersion and use thereof |
| JP2013215953A Active JP6142418B2 (en) | 2013-02-27 | 2013-10-17 | Carbon black dispersion and use thereof |
| JP2014003158A Active JP6244923B2 (en) | 2013-02-27 | 2014-01-10 | Carbon black dispersion and use thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013125306A Active JP5454725B1 (en) | 2013-02-27 | 2013-06-14 | Carbon black dispersion and use thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014003158A Active JP6244923B2 (en) | 2013-02-27 | 2014-01-10 | Carbon black dispersion and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (3) | JP5454725B1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016088880A1 (en) * | 2014-12-04 | 2016-06-09 | デンカ株式会社 | Conductive composition for electrode, electrode for nonaqueous cell, and nonaqueous cell |
| JP2017069181A (en) * | 2015-09-29 | 2017-04-06 | トヨタ自動車株式会社 | Lithium ion secondary battery |
| EP3168904A1 (en) * | 2015-11-12 | 2017-05-17 | Kansai Paint Co., Ltd. | Conductive paste and mixture paste for lithium ion battery positive electrode |
| JP2017098241A (en) * | 2015-11-12 | 2017-06-01 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode, and mixture material paste for lithium ion battery positive electrode |
| JP2017199621A (en) * | 2016-04-28 | 2017-11-02 | トヨタ自動車株式会社 | Conductive paste for preparing positive electrode of lithium ion secondary battery |
| EP3261155A1 (en) * | 2016-06-22 | 2017-12-27 | Kansai Paint Co., Ltd | Conductive paste and mixture paste for lithium ion battery positive electrode |
| JP2017228412A (en) * | 2016-06-22 | 2017-12-28 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode, and mixture material paste for lithium ion battery positive electrode |
| JP2017228413A (en) * | 2016-06-22 | 2017-12-28 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode, and mixture material paste for lithium ion battery positive electrode |
| EP3340255B1 (en) | 2015-09-25 | 2020-02-12 | LG Chem, Ltd. | Carbon black dispersion solution and manufacturing method thereof |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6184902B2 (en) * | 2014-05-30 | 2017-08-23 | 花王株式会社 | Carbon black dispersion |
| JP6303832B2 (en) * | 2014-06-04 | 2018-04-04 | 東洋インキＳｃホールディングス株式会社 | Carbon black dispersion and use thereof |
| JP6645040B2 (en) * | 2014-06-19 | 2020-02-12 | 日本ゼオン株式会社 | Conductive material dispersion for electrochemical element, slurry for positive electrode of electrochemical element, positive electrode for electrochemical element, and electrochemical element |
| JP2016021391A (en) * | 2014-06-19 | 2016-02-04 | 日本ゼオン株式会社 | Conductive material fluid dispersion for electrochemical devices, slurry for electrochemical device positive electrodes, positive electrode for electrochemical devices, and electrochemical device |
| JP6709586B2 (en) * | 2014-08-26 | 2020-06-17 | 東洋インキＳｃホールディングス株式会社 | Carbon black dispersion and its use |
| JP6166235B2 (en) | 2014-08-26 | 2017-07-19 | 大日精化工業株式会社 | Coating liquid, coating film, and composite material |
| KR101966279B1 (en) | 2015-02-12 | 2019-04-05 | 주식회사 엘지화학 | Carbon black dispersion and method of preparing the same |
| JP6720488B2 (en) * | 2015-09-08 | 2020-07-08 | 株式会社豊田自動織機 | Method for producing a composition containing a plurality of positive electrode active materials, a conductive auxiliary agent, a binder and a solvent |
| JP6300774B2 (en) * | 2015-11-12 | 2018-03-28 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode and composite paste for lithium ion battery positive electrode |
| JP6731724B2 (en) * | 2015-12-24 | 2020-07-29 | 関西ペイント株式会社 | Pigment paste and coating material |
| JP6430472B2 (en) | 2016-01-15 | 2018-11-28 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode and composite paste for lithium ion battery positive electrode |
| JP6356164B2 (en) * | 2016-01-15 | 2018-07-11 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode and composite paste for lithium ion battery positive electrode |
| JP6569548B2 (en) * | 2016-01-29 | 2019-09-04 | 東洋インキＳｃホールディングス株式会社 | Method for producing carbon black dispersion for lithium ion secondary battery |
| JP6623808B2 (en) * | 2016-02-12 | 2019-12-25 | 株式会社豊田自動織機 | Slurry for negative electrode and method for producing negative electrode |
| JP6718196B2 (en) * | 2016-03-18 | 2020-07-08 | 関西ペイント株式会社 | Conductive pigment paste and coating material |
| JP6718195B2 (en) * | 2016-03-18 | 2020-07-08 | 関西ペイント株式会社 | Conductive pigment paste and coating material |
| JP6819220B2 (en) * | 2016-10-28 | 2021-01-27 | 日産自動車株式会社 | Negative electrode for electrical devices and electrical devices using them |
| EP3355384A1 (en) * | 2017-01-31 | 2018-08-01 | Universite De Liege | Flexible thin-films for battery electrodes |
| JP7185997B2 (en) * | 2017-07-18 | 2022-12-08 | 関西ペイント株式会社 | Conductive paste for lithium-ion battery positive electrode and method for producing mixture paste for lithium-ion battery positive electrode |
| CN108306020A (en) * | 2018-01-26 | 2018-07-20 | 山东德朗能新能源科技有限公司 | A kind of dispersing method of lithium ion battery conductive agent |
| WO2020137403A1 (en) * | 2018-12-27 | 2020-07-02 | 日本ゼオン株式会社 | Carbon material dispersion liquid for secondary battery electrodes, slurry composition for secondary battery electrodes, electrode for secondary batteries, and secondary battery |
| CN113613768A (en) | 2019-03-29 | 2021-11-05 | 东洋油墨Sc控股株式会社 | Dispersant, dispersion, resin composition, composite material slurry, electrode film, and nonaqueous electrolyte secondary battery |
| JP6831896B1 (en) * | 2019-11-27 | 2021-02-17 | 関西ペイント株式会社 | Conductive pigment pastes, coating materials, and conductive coating films |
| JP7216344B2 (en) | 2020-01-31 | 2023-02-01 | 東洋インキＳｃホールディングス株式会社 | Dispersants, conductive material dispersions, and slurries for electrode films |
| JP6933285B1 (en) | 2020-09-03 | 2021-09-08 | 東洋インキＳｃホールディングス株式会社 | Conductive material dispersion, binder resin-containing conductive material dispersion, electrode film slurry, electrode film, and non-aqueous electrolyte secondary battery |
| JP6962428B1 (en) | 2020-09-03 | 2021-11-05 | 東洋インキＳｃホールディングス株式会社 | Conductive material dispersion, binder resin-containing conductive material dispersion, electrode film slurry, electrode film, and non-aqueous electrolyte secondary battery |
| EP4234637A4 (en) | 2020-12-04 | 2024-05-01 | Denka Company Ltd | Carbon black, slurry, and lithium-ion secondary battery |
| US20240002670A1 (en) | 2020-12-04 | 2024-01-04 | Denka Company Limited | Carbon black, slurry, and lithium ion secondary battery |
| US20240006615A1 (en) | 2020-12-04 | 2024-01-04 | Denka Company Limited | Carbon black, slurry, and lithium-ion secondary battery |
| JPWO2022118921A1 (en) | 2020-12-04 | 2022-06-09 | ||
| JP6850936B1 (en) * | 2020-12-24 | 2021-03-31 | 関西ペイント株式会社 | Conductive pigment pastes, coating materials, and conductive coating films |
| JP2023058303A (en) * | 2021-10-13 | 2023-04-25 | 旭カーボン株式会社 | Mixed carbon black and electrode slurry |
| WO2023167275A1 (en) * | 2022-03-03 | 2023-09-07 | 関西ペイント株式会社 | Electroconductive paste, mixed material paste, electrode for lithium-ion battery positive electrode, and battery |
| JP2023175318A (en) * | 2022-05-30 | 2023-12-12 | 信越化学工業株式会社 | Carbon black dispersion composition for battery, composite paste for positive electrode, positive electrodes for lithium ion secondary battery, and lithium ion secondary battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002110145A (en) * | 2000-10-04 | 2002-04-12 | Matsushita Electric Ind Co Ltd | Nonaqueous secondary battery |
| JP2009123463A (en) * | 2007-11-14 | 2009-06-04 | Sony Corp | Positive electrode for lithium-ion secondary battery, method of manufacturing the same, and lithium-ion secondary battery |
| WO2011024799A1 (en) * | 2009-08-27 | 2011-03-03 | 大日精化工業株式会社 | Aqueous coating liquid for an electrode plate, electrode plate for an electrical storage device, method for manufacturing an electrode plate for an electrical storage device, and electrical storage device |
| JP2011070908A (en) * | 2009-09-25 | 2011-04-07 | Mikuni Color Ltd | Conductive material dispersion liquid, electrode paste, and conductive material coating active substance |
| JP2012243522A (en) * | 2011-05-18 | 2012-12-10 | Toyota Motor Corp | Material for forming positive electrode mixture layer of nonaqueous electrolyte secondary battery and method for manufacturing nonaqueous electrolyte secondary battery |
| WO2014046078A1 (en) * | 2012-09-18 | 2014-03-27 | 株式会社クレハ | Binder for nonaqueous electrolyte secondary cell, binder solution for nonaqueous electrolyte secondary cell, anode mixture for nonaqueous electrolyte secondary cell, and uses thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3122402B2 (en) * | 1997-11-05 | 2001-01-09 | 冨士色素株式会社 | Water-based black pigment ink for white plate |
| JP4525142B2 (en) * | 2003-04-02 | 2010-08-18 | 三菱化学株式会社 | Polyvinyl alcohol block copolymer and aqueous pigment dispersion using the same |
| JP5320394B2 (en) * | 2008-06-02 | 2013-10-23 | 大日精化工業株式会社 | Coating liquid, electrode plate manufacturing coating liquid, undercoat agent and use thereof |
| JP5533057B2 (en) * | 2010-03-11 | 2014-06-25 | 東洋インキＳｃホールディングス株式会社 | Carbon black dispersion |
-
2013
- 2013-06-14 JP JP2013125306A patent/JP5454725B1/en active Active
- 2013-10-17 JP JP2013215953A patent/JP6142418B2/en active Active
-
2014
- 2014-01-10 JP JP2014003158A patent/JP6244923B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002110145A (en) * | 2000-10-04 | 2002-04-12 | Matsushita Electric Ind Co Ltd | Nonaqueous secondary battery |
| JP2009123463A (en) * | 2007-11-14 | 2009-06-04 | Sony Corp | Positive electrode for lithium-ion secondary battery, method of manufacturing the same, and lithium-ion secondary battery |
| WO2011024799A1 (en) * | 2009-08-27 | 2011-03-03 | 大日精化工業株式会社 | Aqueous coating liquid for an electrode plate, electrode plate for an electrical storage device, method for manufacturing an electrode plate for an electrical storage device, and electrical storage device |
| JP2011070908A (en) * | 2009-09-25 | 2011-04-07 | Mikuni Color Ltd | Conductive material dispersion liquid, electrode paste, and conductive material coating active substance |
| JP2012243522A (en) * | 2011-05-18 | 2012-12-10 | Toyota Motor Corp | Material for forming positive electrode mixture layer of nonaqueous electrolyte secondary battery and method for manufacturing nonaqueous electrolyte secondary battery |
| WO2014046078A1 (en) * | 2012-09-18 | 2014-03-27 | 株式会社クレハ | Binder for nonaqueous electrolyte secondary cell, binder solution for nonaqueous electrolyte secondary cell, anode mixture for nonaqueous electrolyte secondary cell, and uses thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016088880A1 (en) * | 2014-12-04 | 2016-06-09 | デンカ株式会社 | Conductive composition for electrode, electrode for nonaqueous cell, and nonaqueous cell |
| EP3340255B1 (en) | 2015-09-25 | 2020-02-12 | LG Chem, Ltd. | Carbon black dispersion solution and manufacturing method thereof |
| JP2017069181A (en) * | 2015-09-29 | 2017-04-06 | トヨタ自動車株式会社 | Lithium ion secondary battery |
| EP3168904A1 (en) * | 2015-11-12 | 2017-05-17 | Kansai Paint Co., Ltd. | Conductive paste and mixture paste for lithium ion battery positive electrode |
| JP2017098241A (en) * | 2015-11-12 | 2017-06-01 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode, and mixture material paste for lithium ion battery positive electrode |
| US10256472B2 (en) | 2015-11-12 | 2019-04-09 | Kansai Paint Co., Ltd. | Conductive paste and mixture paste for lithium ion battery positive electrode |
| JP2017199621A (en) * | 2016-04-28 | 2017-11-02 | トヨタ自動車株式会社 | Conductive paste for preparing positive electrode of lithium ion secondary battery |
| EP3261155A1 (en) * | 2016-06-22 | 2017-12-27 | Kansai Paint Co., Ltd | Conductive paste and mixture paste for lithium ion battery positive electrode |
| JP2017228412A (en) * | 2016-06-22 | 2017-12-28 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode, and mixture material paste for lithium ion battery positive electrode |
| JP2017228413A (en) * | 2016-06-22 | 2017-12-28 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode, and mixture material paste for lithium ion battery positive electrode |
| US10468683B2 (en) | 2016-06-22 | 2019-11-05 | Kansai Paint Co., Ltd. | Conductive paste and mixture paste for lithium ion battery positive electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014193986A (en) | 2014-10-09 |
| JP6142418B2 (en) | 2017-06-07 |
| JP6244923B2 (en) | 2017-12-13 |
| JP5454725B1 (en) | 2014-03-26 |
| JP2014194001A (en) | 2014-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5454725B1 (en) | Carbon black dispersion and use thereof | |
| JP6709586B2 (en) | Carbon black dispersion and its use | |
| JP6303832B2 (en) | Carbon black dispersion and use thereof | |
| JP6142415B2 (en) | Carbon black dispersion and use thereof | |
| JP5533057B2 (en) | Carbon black dispersion | |
| JP5499040B2 (en) | Aqueous slurry composition, electrode plate for power storage device, and power storage device | |
| KR102217137B1 (en) | Carbon black dispersion and use thereof | |
| WO2021220773A1 (en) | Conductive material dispersion, method for producing same, composition for secondary battery electrodes using same, electrode membrane, secondary battery and vehicle | |
| JP5601416B1 (en) | Carbon black dispersion and use thereof | |
| WO2014132809A1 (en) | Carbon black dispersion and use thereof | |
| JP6879150B2 (en) | Conductive aid dispersion, its use and its manufacturing method | |
| JP6569548B2 (en) | Method for producing carbon black dispersion for lithium ion secondary battery | |
| KR20210071086A (en) | bookbinder | |
| JP2024045445A (en) | Carbon nanotube dispersion and its use | |
| Piffet et al. | Aqueous processing of flexible, free-standing Li4Ti5O12 electrodes for Li-ion batteries | |
| JP2018206579A (en) | Carbon black slurry for electrode, composition for forming electrode, and manufacturing method of electrode for lithium ion secondary battery | |
| JP7059858B2 (en) | Carbon black dispersion composition and its use | |
| JP2020021629A (en) | Carbon black dispersion composition for battery and use thereof | |
| CN112640155A (en) | Electrode for secondary battery and secondary battery | |
| JP2019220401A (en) | Carbon black slurry for electrode and composition for forming electrode | |
| JP7339404B2 (en) | Dispersant composition for electricity storage device electrode | |
| JP7390516B1 (en) | Composite for secondary battery electrodes | |
| JP7414171B1 (en) | Carbon nanotube dispersion composition and its use | |
| WO2023127917A1 (en) | Dispersant composition for power storage device electrodes | |
| JP2024003640A (en) | Conductive material dispersion, and mixture composition for secondary battery electrode using the same, electrode film, secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150219 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150219 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160411 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170410 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170418 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20170419 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170419 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20170419 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6142418 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |