JP2011192620A - Method of manufacturing carbon black dispersion for lithium ion secondary battery electrode - Google Patents
Method of manufacturing carbon black dispersion for lithium ion secondary battery electrode Download PDFInfo
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- JP2011192620A JP2011192620A JP2010060147A JP2010060147A JP2011192620A JP 2011192620 A JP2011192620 A JP 2011192620A JP 2010060147 A JP2010060147 A JP 2010060147A JP 2010060147 A JP2010060147 A JP 2010060147A JP 2011192620 A JP2011192620 A JP 2011192620A
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- Japan
- Prior art keywords
- electrode
- carbon black
- lithium ion
- secondary battery
- ion secondary
- 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.)
- Pending
Links
- 239000006229 carbon black Substances 0.000 title claims abstract description 82
- 239000006185 dispersion Substances 0.000 title claims abstract description 75
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000000203 mixture Substances 0.000 claims abstract description 65
- 229920000642 polymer Polymers 0.000 claims abstract description 51
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000004898 kneading Methods 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 16
- 239000011149 active material Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- 235000019241 carbon black Nutrition 0.000 description 72
- 230000000052 comparative effect Effects 0.000 description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 33
- 238000011156 evaluation Methods 0.000 description 33
- 239000002245 particle Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000011888 foil Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 239000002482 conductive additive Substances 0.000 description 9
- -1 lithium transition metal Chemical class 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229920006369 KF polymer Polymers 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000002296 dynamic light scattering Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- IPBFYZQJXZJBFQ-UHFFFAOYSA-N gamma-octalactone Chemical compound CCCCC1CCC(=O)O1 IPBFYZQJXZJBFQ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- DRLFMBDRBRZALE-UHFFFAOYSA-N melatonin Chemical compound COC1=CC=C2NC=C(CCNC(C)=O)C2=C1 DRLFMBDRBRZALE-UHFFFAOYSA-N 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-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
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- 241000557626 Corvus corax Species 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- 101000713585 Homo sapiens Tubulin beta-4A chain Proteins 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 102100036788 Tubulin beta-4A chain Human genes 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N ethylene glycol dimethyl ether Natural products COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 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
- 239000003960 organic solvent Substances 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
- 239000003973 paint Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000011029 spinel Chemical group 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000010936 titanium Substances 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、リチウムイオン二次電池を構成する電極に使用するカーボンブラック分散体の製造方法に関する。また、該分散体を使用して電極合材層が形成された電池用電極、および正極および負極の少なくとも一方が該電極であるリチウムイオン二次電池の製造方法に関する。 The present invention relates to a method for producing a carbon black dispersion used for an electrode constituting a lithium ion secondary battery. The present invention also relates to a battery electrode in which an electrode mixture layer is formed using the dispersion, and a method for producing a lithium ion secondary battery in which at least one of a positive electrode and a negative electrode is the electrode.
近年、デジタルカメラや携帯電話のような小型携帯型電子機器が広く用いられるようになってきた。これらの電子機器には、容積を最小限にし、かつ重量を軽くすることが常に求められてきており、搭載される電池においても、小型、軽量かつ大容量の電池の実現が求められている。また、自動車搭載用などの大型二次電池においても、従来の鉛蓄電池に代えて、大型の非水電解質二次電池の実現が望まれている。 In recent years, small portable electronic devices such as digital cameras and mobile phones have been widely used. These electronic devices have always been required to minimize the volume and reduce the weight, and the batteries to be mounted are also required to be small, light, and have a large capacity. Also, in large-sized secondary batteries for automobiles and the like, it is desired to realize a large non-aqueous electrolyte secondary battery instead of a conventional lead-acid battery.
そのような要求に応えるため、リチウムイオン二次電池の開発が活発に行われている。リチウムイオン二次電池の電極としては、リチウムイオンを含む正極活物質と導電助剤と有機バインダーなどからなる電極合材を金属箔の集電体の表面に固着させた正極、及び、リチウムイオンの脱挿入可能な負極活物質と導電助剤と有機バインダーなどからなる電極合材を金属箔の集電体の表面に固着させた負極が使用されている。 In order to meet such demands, lithium ion secondary batteries are being actively developed. As an electrode of a lithium ion secondary battery, a positive electrode in which an electrode mixture composed of a positive electrode active material containing lithium ions, a conductive additive, an organic binder, and the like is fixed to the surface of a current collector of metal foil, and a lithium ion A negative electrode is used in which an electrode mixture made of a removable negative electrode active material, a conductive additive, an organic binder, and the like is fixed to the surface of a current collector of a metal foil.
一般的に、正極活物質としては、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が用いられているが、これらは電子伝導性が低く、単独での使用では十分な電池性能が得られない。そこで、カーボンブラック（例えば、アセチレンブラック）やグラファイト（黒鉛）等の炭素材料を導電助剤として添加することで導電性を改善し、電極の内部抵抗を低減することが試みられている。 In general, lithium transition metal composite oxides such as lithium cobaltate and lithium manganate are used as the positive electrode active material, but these have low electronic conductivity and have sufficient battery performance when used alone. I can't get it. Therefore, attempts have been made to improve the conductivity and reduce the internal resistance of the electrode by adding a carbon material such as carbon black (for example, acetylene black) or graphite (graphite) as a conductive aid.
一方、負極活物質としては、通常黒鉛が用いられている。黒鉛はそれ自身が導電性を有しているものの、黒鉛とともに導電助剤としてアセチレンブラック等のカーボンブラックを添加すると充放電特性が改善されることが知られている。これは、一般に用いられる黒鉛粒子は大きいために、黒鉛単独で使用すると電極層に充填された時の隙間が多くなってしまうが、導電助剤としてカーボンブラックを併用した場合は、微細なカーボンブラック粒子が黒鉛粒子間の隙間を埋めることで接触面積が増え、抵抗が下がるためではないかと思われる。しかしながら、この場合も導電助剤の分散が不十分であると、導電効果が低減する。 On the other hand, graphite is usually used as the negative electrode active material. Although graphite itself has conductivity, it is known that charge and discharge characteristics are improved by adding carbon black such as acetylene black as a conductive aid together with graphite. This is because the graphite particles generally used are large, so if graphite alone is used, the gap when filled in the electrode layer will increase. However, when carbon black is used as a conductive additive, fine carbon black is used. It seems that the contact area increases by filling the gaps between the graphite particles and the resistance decreases. However, in this case as well, the conductive effect is reduced if the dispersion of the conductive aid is insufficient.
電極の内部抵抗を低減することは、大電流での放電を可能とすることや、充放電の効率を向上させる上で非常に重要な要素の一つとなっている。しかしながら、導電性に優れた炭素材料（導電助剤）は、ストラクチャーや比表面積が大きいため凝集力が強く、リチウムイオン二次電池の電極合材形成用スラリー中に均一混合・分散することが困難である。そして、導電助剤である炭素材料の分散性や粒度の制御が不十分な場合、均一な導電ネットワークが形成さないために電極の内部抵抗の低減が図れず、その結果、活物質であるリチウム遷移金属複合酸化物やグラファイトなどの性能を十分に引き出せないという問題が生じている。また、電極合材中の導電助剤の分散が不十分であると、部分的凝集に起因して電極板上に抵抗分布が生じ、電池として使用した際に電流が集中し、部分的な発熱および劣化が促進される等の不具合が生ずることがある。 Reducing the internal resistance of the electrode is one of the very important factors in enabling discharge with a large current and improving charge / discharge efficiency. However, carbon materials with excellent electrical conductivity (conducting aids) have high cohesion due to their large structure and specific surface area, making it difficult to uniformly mix and disperse in the electrode mixture forming slurry of a lithium ion secondary battery. It is. And, when the dispersibility and particle size control of the carbon material that is the conductive auxiliary agent are insufficient, the internal resistance of the electrode cannot be reduced because the uniform conductive network is not formed, and as a result, the lithium that is the active material There has been a problem that the performance of transition metal composite oxides and graphite cannot be sufficiently extracted. In addition, if the dispersion of the conductive additive in the electrode mixture is insufficient, resistance distribution occurs on the electrode plate due to partial aggregation, current concentrates when used as a battery, and partial heat generation occurs. In addition, problems such as accelerated deterioration may occur.
また、金属箔などの電極集電体上に電極合材層を形成する場合、多数回充放電を繰り返すと、集電体と電極合材層の界面や、電極合材内部における活物質と導電助剤界面の密着性が悪化し、電池性能が低下する問題がある。これは、充放電におけるリチウムイオンのドープ、脱ドープにより活物質および電極合材層が膨張、収縮を繰り返すために、電極合材層と集電体界面および、活物質と導電助剤界面に局部的なせん断応力が発生し界面の密着性が悪化するためと考えられている。そしてこの場合も、導電助剤の分散が不十分であると、密着低下が著しくなる。これは、粗大な凝集粒子が存在すると、応力が緩和されにくくなるためであると思われる。 In addition, when an electrode mixture layer is formed on an electrode current collector such as a metal foil, repeated charging and discharging a large number of times causes the interface between the current collector and the electrode mixture layer, and the active material and the conductive material inside the electrode mixture. There is a problem in that the adhesion at the auxiliary agent interface is deteriorated and the battery performance is lowered. This is because the active material and the electrode mixture layer are repeatedly expanded and contracted by doping and dedoping of lithium ions during charge and discharge, so that the electrode mixture layer and the current collector interface and the active material and the conductive auxiliary agent interface are localized. This is thought to be due to the generation of shear stress and the deterioration of interfacial adhesion. In this case as well, if the dispersion of the conductive additive is insufficient, the adhesion reduction becomes significant. This is considered to be because when coarse agglomerated particles are present, the stress is hardly relaxed.
さらに、電極合材層は一般的に、正極活物質または負極活物質、導電助剤、バインダー、および溶剤を含む合材ペーストを集電体上に塗工して形成されるが、塗工方法によって適正粘度があり、溶剤量によって合材ペーストの粘度を調整を行う。この場合も導電助剤の分散が不十分であると、同一組成で粘度が高くなり、溶剤量が多く必要となるため、塗工後の乾燥時間が長くなり、乾燥に要するエネルギーコストが増大したり製造速度が低下するなどして生産性が低下してしまうという問題があった。 Further, the electrode mixture layer is generally formed by applying a mixture paste containing a positive electrode active material or a negative electrode active material, a conductive additive, a binder, and a solvent onto a current collector. The viscosity of the composite paste is adjusted by the amount of solvent. In this case as well, if the dispersion of the conductive auxiliary agent is insufficient, the viscosity becomes high with the same composition and a large amount of solvent is required, so that the drying time after coating becomes long and the energy cost required for drying increases. There is a problem that productivity is lowered due to a decrease in manufacturing speed.
このように、リチウムイオン二次電池においては導電助剤である炭素材料の分散が重要なポイントの一つである。特許文献１および特許文献２には導電助剤と結着剤と溶剤をあらかじめ分散し、その後活物質を添加する例が記載されている。しかしながら、導電助剤と結着剤の濃度および比率には言及されておらず、導電助剤の最適な分散条件が提示されていない。また、特許文献１の実施例には主としてボールミルなどのメディア型分散機を使用した場合が記載されているが、メディアとして使用するボールやビーズの摩耗粉がコンタミとして問題になる場合がある。特許文献２に記載されている二軸エクストルーダーは連続的に混練物を製造することができる反面、一定量を長時間混練するには複数回の混練工程を経る必要があり、分散に時間のかかるストラクチャーや比表面積が大きい導電助剤の分散には不向きである。 Thus, in the lithium ion secondary battery, the dispersion of the carbon material that is a conductive auxiliary agent is one of the important points. Patent Document 1 and Patent Document 2 describe examples in which a conductive additive, a binder, and a solvent are dispersed in advance, and then an active material is added. However, the concentration and ratio of the conductive assistant and the binder are not mentioned, and the optimum dispersion conditions for the conductive assistant are not presented. Further, in the example of Patent Document 1, a case where a media type dispersing machine such as a ball mill is mainly used is described. However, wear particles of balls and beads used as media may cause a problem as contamination. Although the biaxial extruder described in Patent Document 2 can continuously produce a kneaded product, it needs to go through a plurality of kneading steps to knead a certain amount for a long time. It is unsuitable for dispersion of a conductive additive having such a structure or a large specific surface area.
また、特許文献３、特許文献４には、カーボンブラックを溶剤に分散する際に、分散剤として界面活性剤を用いる例が記載されている。しかしながら、界面活性剤は炭素材料表面への吸着力が弱いため、良好な分散安定性を得るには界面活性剤の添加量を多くしなければならず、この結果、含有可能な活物質の量が少なくなり、電池容量が低下してしまう。また、界面活性剤の炭素材料への吸着が不十分であると炭素材料が凝集してしまう。一般的に界面活性剤は、水溶液中での分散と比較して有機溶剤中での分散効果が著しく低い。 Patent Documents 3 and 4 describe examples in which a surfactant is used as a dispersant when carbon black is dispersed in a solvent. However, since the surfactant has a weak adsorption force on the surface of the carbon material, it is necessary to increase the amount of the surfactant added in order to obtain good dispersion stability. As a result, the amount of the active material that can be contained Decreases and the battery capacity decreases. Further, if the surfactant is not sufficiently adsorbed on the carbon material, the carbon material will aggregate. In general, a surfactant has a remarkably low dispersion effect in an organic solvent as compared with dispersion in an aqueous solution.
特許文献５および特許文献６には、カーボンブラックを溶剤に分散する際に分散樹脂を添加することでカーボンスラリーの分散状態を改善し、そのカーボンスラリーと、活物質とを混合して、電極用合材を作成する方法が開示されている。しかしながら、この方法では、カーボンブラックの分散性は向上するものの、比表面積の大きな微細なカーボンブラックの分散を行う場合には大量の分散樹脂が必要となること、および分子量の大きな分散樹脂がカーボンブラック表面を被覆してしまうことなどから、導電ネットワークが阻害され電極の抵抗が増大し、結果的にカーボンブラックの分散向上による効果を相殺してしまう場合がある。 In Patent Document 5 and Patent Document 6, the dispersion state of the carbon slurry is improved by adding a dispersion resin when carbon black is dispersed in a solvent, and the carbon slurry and the active material are mixed to form an electrode. A method of making a composite is disclosed. However, although this method improves the dispersibility of carbon black, a large amount of dispersed resin is required to disperse fine carbon black having a large specific surface area, and a dispersed resin having a large molecular weight is carbon black. Since the surface is covered, the conductive network is obstructed and the resistance of the electrode is increased. As a result, the effect of improving the dispersion of carbon black may be offset.
一方、特許文献７には、合材ペースト作製時に溶剤を複数回に分けて添加することで溶剤量を減らしつつ適正粘度に調製する方法が開示されている。しかしながら、乾燥工程時間の短縮は確認されているものの、混練に用いる機械の詳細や電池性能評価結果の記載がなく、この方法では導電助剤を十分に分散することができていないと推測される。 On the other hand, Patent Document 7 discloses a method of adjusting to a proper viscosity while reducing the amount of solvent by adding a solvent in a plurality of times during preparation of a composite paste. However, although it has been confirmed that the drying process time is shortened, there is no description of the details of the machine used for kneading and the battery performance evaluation results, and it is assumed that the conductive auxiliary agent cannot be sufficiently dispersed by this method. .
以上のような問題に鑑み、本発明は、カーボンブラックの導電性を阻害せずに分散安定化を図ることにより、これを用いて作製されるリチウムイオン二次電池の電池性能を向上させるとともに、生産性を向上させることを目的とする。
本発明者らは、上記目的を達成するため鋭意検討を行った結果、Ｎ−メチル−２−ピロリドンが全重量の２０重量％〜６０重量％、かつ、フッ化ビニリデン系ポリマーの重量がカーボンブラックの重量以下で、カーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンとを混練することにより、分散安定性に優れるリチウムイオン二次電池電極用カーボンブラック分散体を調製できることを見出した。特に、混練工程に２本ロールミルを使用することで、電極の低抵抗化および、電極集電体と電極合材もしくは、活物質と導電助剤との密着性の向上に起因すると思われる電池性能向上効果を見出し、本発明をなすに至ったものである。 As a result of intensive studies to achieve the above object, the present inventors have found that N-methyl-2-pyrrolidone is 20% to 60% by weight of the total weight, and that the weight of the vinylidene fluoride polymer is carbon black. It was found that a carbon black dispersion for a lithium ion secondary battery electrode having excellent dispersion stability can be prepared by kneading carbon black, a vinylidene fluoride polymer, and N-methyl-2-pyrrolidone at a weight less than . In particular, by using a two-roll mill for the kneading process, the battery performance is considered to be due to the reduction in the resistance of the electrode and the improvement in the adhesion between the electrode current collector and the electrode mixture or the active material and the conductive additive. The improvement effect has been found and the present invention has been achieved.
すなわち、本発明は、カーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンとを混練してなるリチウムイオン二次電池電極用カーボンブラック分散体の製造方法であって、Ｎ−メチル−２−ピロリドンが該分散体の２０重量％〜６０重量％、かつ、フッ化ビニリデン系ポリマーの重量がカーボンブラックの重量以下で混練することを特徴とする製造方法に関する。
また、本発明は、混練工程に２本ロールミルを使用することを特徴とする、上記のリチウムイオン二次電池電極用カーボンブラック分散体の製造方法に関する。
また、本発明は、粉末状のフッ化ビニリデン系ポリマーを使用することを特徴とする、上記のリチウムイオン二次電池電極用カーボンブラック分散体の製造方法に関する。
That is, the present invention relates to a method for producing a carbon black dispersion for a lithium ion secondary battery electrode obtained by kneading carbon black, a vinylidene fluoride-based polymer, and N-methyl-2-pyrrolidone. The present invention relates to a production method characterized in that 2-pyrrolidone is kneaded in an amount of 20% to 60% by weight of the dispersion, and the weight of the vinylidene fluoride polymer is equal to or less than the weight of carbon black.
The present invention also relates to the above-described method for producing a carbon black dispersion for a lithium ion secondary battery electrode, wherein a two-roll mill is used in the kneading step.
The present invention also relates to a method for producing the carbon black dispersion for a lithium ion secondary battery electrode, wherein a powdered vinylidene fluoride polymer is used.
また、本発明は、上記の製造方法で製造されてなるリチウムイオン二次電池電極用カーボンブラック分散体に関する。 Moreover, this invention relates to the carbon black dispersion for lithium ion secondary battery electrodes manufactured with said manufacturing method.
さらに、本発明は、上記の分散体と正極活物質または負極活物質とを混合することを特徴とする、リチウムイオン二次電池電極用合材ペーストの製造方法に関する。
さらに、本発明は、上記の分散体と正極活物質または負極活物質とフッ化ビニリデン系ポリマーとを混合することを特徴とする、リチウムイオン二次電池電極用合材ペーストの製造方法に関する。
Furthermore, this invention relates to the manufacturing method of the lithium ion secondary battery electrode compound material paste characterized by mixing said dispersion, and a positive electrode active material or a negative electrode active material.
Furthermore, this invention relates to the manufacturing method of the lithium ion secondary battery electrode compound paste characterized by mixing said dispersion | distribution, a positive electrode active material, or a negative electrode active material, and a vinylidene fluoride type polymer.
また、本発明は、上記の製造方法で製造されてなるリチウムイオン二次電池電極用合材ペーストに関する。 The present invention also relates to a composite paste for lithium ion secondary battery electrodes produced by the above production method.
さらに、本発明は、上記の分散体を使用して電極下地層が形成された電池用電極に関する。
さらに、本発明は、上記の合材ペーストを使用して電極合材層が形成された電池用電極に関する。
さらに、本発明は、集電体上に正極合材層を有する正極と、集電体上に負極合材層を有する負極と、リチウムを含む電解質とを具備するリチウム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、上記の電池用電極であるリチウムイオン二次電池に関する。
Furthermore, this invention relates to the battery electrode in which the electrode base layer was formed using said dispersion.
Furthermore, this invention relates to the battery electrode in which the electrode compound-material layer was formed using said compound-material paste.
Furthermore, 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. In addition, the present invention relates to a lithium ion secondary battery in which at least one of a positive electrode and a negative electrode is the battery electrode.
本発明の好ましい実施態様によれば、リチウムイオン二次電池電極用カーボンブラック分散体において、カーボンブラックの導電性を阻害することなく分散安定化が図られているため、これを用いて作製されるリチウムイオン二次電池の電池性能を向上させるとともに、生産性を向上させることができる。 According to a preferred embodiment of the present invention, in the carbon black dispersion for lithium ion secondary battery electrodes, the dispersion stabilization is achieved without hindering the conductivity of the carbon black. While improving the battery performance of a lithium ion secondary battery, productivity can be improved.
本発明におけるリチウムイオン二次電池電極用カーボンブラック分散体の製造方法は、Ｎ−メチル−２−ピロリドンが全重量の２０重量％〜６０重量％、かつ、フッ化ビニリデン系ポリマーの重量がカーボンブラックの重量以下で、カーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンとを混練することを特徴とするが、以下にその詳細を説明する。 The method for producing a carbon black dispersion for a lithium ion secondary battery electrode according to the present invention is such that N-methyl-2-pyrrolidone is 20 wt% to 60 wt% of the total weight, and the weight of the vinylidene fluoride polymer is carbon black. The carbon black, the vinylidene fluoride polymer, and N-methyl-2-pyrrolidone are kneaded at a weight less than the above weight, and the details will be described below.
＜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 or hollow carbon can be used.
カーボンの酸化処理は、カーボン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より、例えばフェノール基、キノン基、カルボキシル基、カルボニル基の様な酸素含有極性官能基をカーボン表面に直接導入（共有結合）する処理であり、カーボンの分散性を向上させるために一般的に行われている。しかしながら、官能基の導入量が多くなる程カーボンの導電性が低下することが一般的であるため、酸化処理をしていないカーボンの使用が好ましい。 The oxidation treatment of carbon is performed by treating carbon at a high temperature in the air or by secondary treatment with nitric acid, nitrogen dioxide, ozone, etc., for example, such as phenol group, quinone group, carboxyl group, carbonyl group. This is a treatment for directly introducing (covalently bonding) an oxygen-containing polar functional group to the carbon surface, and is generally performed to improve the dispersibility of carbon. However, since it is common for the conductivity of carbon to fall, so that the introduction amount of a functional group increases, it is preferable to use the carbon which has not been oxidized.
用いるカーボンブラックの比表面積は、値が大きいほど、カーボンブラック粒子どうしの接触点が増えるため、電極の内部抵抗を下げるのに有利となる。具体的には、窒素の吸着量から求められる比表面積（ＢＥＴ）で、２０ｍ２／ｇ以上、１５００ｍ２／ｇ以下、好ましくは５０ｍ２／ｇ以上、１５００ｍ２／ｇ以下、更に好ましくは１００ｍ２／ｇ以上、１５００ｍ２／ｇ以下のものを使用することが望ましい。比表面積が２０ｍ２／ｇを下回るカーボンブラックを用いると、十分な導電性を得ることが難しくなる場合があり、１５００ｍ２／ｇを超えるカーボンブラックは、市販材料での入手が困難となる場合がある。 As the specific surface area of the carbon black used increases, the number of contact points between the carbon black particles increases, which is advantageous in reducing the internal resistance of the electrode. Specifically, the specific surface area (BET) determined from the adsorption amount of nitrogen is 20 m 2 / g or more and 1500 m 2 / g or less, preferably 50 m 2 / g or more and 1500 m 2 / g or less, more preferably 100 m 2. / G or more and 1500 m 2 / g or less are desirable. When carbon black having a specific surface area of less than 20 m 2 / g is used, it may be difficult to obtain sufficient conductivity, and carbon black of more than 1500 m 2 / g may be difficult to obtain from commercially available materials. is there.
また、用いるカーボンブラックの粒径は、一次粒子径で０．００５〜１μｍが好ましく、特に、０．０１〜０．２μｍが好ましい。ただし、ここでいう一次粒子径とは、電子顕微鏡などで測定された粒子径を平均したものである。 Further, the particle size of the carbon black to be used is preferably 0.005 to 1 μm, particularly preferably 0.01 to 0.2 μm in terms of primary particle size. However, the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.
市販のカーボンブラックとしては、例えば、トーカブラック＃４３００、＃４４００、＃４５００、＃５５００等（東海カーボン社製、ファーネスブラック）、プリンテックスＬ等（デグサ社製、ファーネスブラック）、Ｒａｖｅｎ７０００、５７５０、５２５０、５０００ＵＬＴＲＡIII、５０００ＵＬＴＲＡ等、Ｃｏｎｄｕｃｔｅｘ ＳＣ ＵＬＴＲＡ、Ｃｏｎｄｕｃｔｅｘ ９７５ ＵＬＴＲＡ等（コロンビヤン社製、ファーネスブラック）、＃２３５０、＃２４００Ｂ、＃３００５０Ｂ、＃３０３０Ｂ、＃３２３０Ｂ、＃３３５０Ｂ、＃３４００Ｂ、＃５４００Ｂ等（三菱化学社製、ファーネスブラック）、ＭＯＮＡＲＣＨ１４００、１３００、９００、ＶｕｌｃａｎＸＣ−７２Ｒ、ＢｌａｃｋＰｅａｒｌｓ２０００等（キャボット社製、ファーネスブラック）、Ｅｎｓａｃｏ２５０Ｇ、Ｅｎｓａｃｏ２６０Ｇ、Ｅｎｓａｃｏ３５０Ｇ、ＳｕｐｅｒＰ−Ｌｉ（ＴＩＭＣＡＬ社製）、ケッチェンブラックＥＣ−３００Ｊ、ＥＣ−６００ＪＤ（アクゾ社製）、デンカブラック、デンカブラックＨＳ−１００、ＦＸ−３５（電気化学工業社製、アセチレンブラック）等が挙げられるが、これらに限定されるものではない。 Examples of commercially available carbon black include Toka Black # 4300, # 4400, # 4500, # 5500 (Tokai Carbon Co., Furnace Black), Printex L and the like (Degussa Co., Furnace Black), Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULTRA, etc., Conductex SC ULTRA, Conductex 975 ULTRA, etc. (Columbian manufactured by Furnace Black), # 2350, # 2400B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B, # 5400B, etc. (Manufactured by Chemical Co., Furnace Black), MONARCH1400, 1300, 900, VulcanXC-72R, BlackPearls2000, etc. Fans Black), Ensaco 250G, Ensaco 260G, Ensaco 350G, SuperP-Li (manufactured by TIMCAL), Ketjen Black EC-300J, EC-600JD (manufactured by Akzo), Denka Black, Denka Black HS-100, FX-35 (Electrochemical Industry) However, it is not limited to these.
＜フッ化ビニリデン系ポリマー＞
一般的に、リチウムイオン二次電池にはバインダーとしてフッ化ビニリデン系ポリマーが用いられており、本発明においても好適に用いられる。
<Vinylidene fluoride polymer>
In general, a vinylidene fluoride polymer is used as a binder in a lithium ion secondary battery, and is preferably used in the present invention.
フッ化ビニリデン系ポリマーとしては、例えば、ポリフッ化ビニリデン（ホモポリマー）、フッ化ビニリデンとヘキサフルオロプロピレンのコポリマー、およびそれらに官能基を導入したもの等が挙げられるが、これらに限定されるものではない。また、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。 Examples of the vinylidene fluoride polymer include, but are not limited to, polyvinylidene fluoride (homopolymer), a copolymer of vinylidene fluoride and hexafluoropropylene, and those having a functional group introduced thereto. Absent. Various commercial products and synthetic products can be used alone or in combination of two or more.
フッ化ビニリデン系ポリマーの重量平均分子量は２０万〜１１０万が好ましく、６０万〜１１０万がさらに好ましい。分子量が２０万未満のものは結着性が悪いため、電極合材層内のバインダー比率を増やして結着性を向上させると容量が低下し、比率を変えなければ電極合材層と集電体との密着性が低下する場合がある。分子量が１１０万を超えると、Ｎ−メチル−２−ピロリドンに対する溶解度が低くなるため、好適な性状のペーストを得ることが困難な場合がある。 The weight average molecular weight of the vinylidene fluoride polymer is preferably 200,000 to 1,100,000, and more preferably 600,000 to 1,100,000. When the molecular weight is less than 200,000, the binding property is poor. Therefore, increasing the binder ratio in the electrode mixture layer to improve the binding property decreases the capacity. If the ratio is not changed, the electrode mixture layer and the current collector Adhesion with the body may be reduced. When the molecular weight exceeds 1.1 million, the solubility in N-methyl-2-pyrrolidone is lowered, and it may be difficult to obtain a paste having suitable properties.
フッ化ビニリデン系ポリマーはＮ−メチル−２−ピロリドン溶液として流通する場合があるが、本発明には粉末状のものを用いる方が好ましい。一般的にフッ化ビニリデン系ポリマーのＮ−メチル−２−ピロリドン溶液はＮ−メチル−２−ピロリドンの含有量が多いため、本発明のカーボンブラック分散体における適正濃度、組成比に調製することが困難な場合がある。 Although the vinylidene fluoride polymer may be distributed as an N-methyl-2-pyrrolidone solution, it is preferable to use a powdery polymer in the present invention. In general, an N-methyl-2-pyrrolidone solution of a vinylidene fluoride polymer has a high content of N-methyl-2-pyrrolidone, so that it can be prepared to have an appropriate concentration and composition ratio in the carbon black dispersion of the present invention. It can be difficult.
市販のフッ化ビニリデン系ポリマーとしては、例えば、ＫＦポリマーＷ＃１１００、＃１３００、＃１７００、＃７２００、＃７３００、＃９１００、＃９２００、＃９３００（クレハ社製）、カイナー７２１、７４１、７６１、４６１、３０１Ｆ、ＨＳＶ９００、カイナーフレックス２８５１、２８０１、２８２１（アルケマ社製）、ソレフ１０１３、１０１５、２１２１６、３１５０８、６０２０（ソルベイソレクシス社製）等が挙げられるが、これらに限定されるものではない。 Examples of commercially available vinylidene fluoride-based polymers include KF polymers W # 1100, # 1300, # 1700, # 7200, # 7300, # 9100, # 9200, # 9300 (manufactured by Kureha Co., Ltd.), Kyner 721, 741, 761. 461, 301F, HSV900, Kyner Flex 2851, 2801, 2821 (Arkema), Solef 1013, 1015, 21216, 31508, 6020 (Solve Solexis), etc., but are not limited thereto. Absent.
＜Ｎ−メチル−２−ピロリドン＞
本発明にはＮ−メチル−２−ピロリドンが好適に用いられる。Ｎ−メチル−２−ピロリドンはラクタム構造を含む５員環の構造を持つ有機化合物で、ジメチルホルムアミドやジメチルアセトアミド、ジメチルスルホキシド等と同じく非プロトン性極性溶媒に属する。高い溶解性を持ち、フッ化ビニリデン系ポリマーを溶解することができるため、一般的にリチウムイオン二次電池の電極製造に用いられている。
<N-methyl-2-pyrrolidone>
In the present invention, N-methyl-2-pyrrolidone is preferably used. N-methyl-2-pyrrolidone is an organic compound having a 5-membered ring structure including a lactam structure, and belongs to an aprotic polar solvent like dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like. Since it has high solubility and can dissolve a vinylidene fluoride-based polymer, it is generally used for manufacturing an electrode of a lithium ion secondary battery.
＜正極活物質及び負極活物質＞
本発明に用いる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ポリマー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。
<Positive electrode active material and negative electrode active material>
The positive electrode active material used in the present invention is not particularly limited, and metal oxides capable of doping or intercalating lithium ions, metal compounds such as metal sulfides, and conductive polymers can be used. 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, transition metal sulfide powders such as TiS 2 and FeS, and the like. 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.
本発明に用いる負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Li、またはその合金、スズ合金、シリコン合金負極、ＬｉＸＦｅ２Ｏ３、ＬｉＸＦｅ３Ｏ４、ＬｉＸＷＯ２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、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用いられる。 There are no particular limitations on the negative electrode active material used in the present invention, lithium ion doping or capable of intercalating Li metal or its alloy, tin alloy, silicon alloy negative electrode, Li X Fe 2 O 3, Li X Fe 3 Manufacture of amorphous carbonaceous materials such as metal oxides such as O 4 and Li X WO 2 , conductive polymers such as polyacetylene and poly-p-phenylene, soft carbon and hard carbon, and highly graphitized carbon materials Carbon-based powders such as graphite or natural graphite, carbon black, mesophase carbon black, resin-fired carbon materials, gas-grown carbon fibers, carbon fibers and the like are used.
＜カーボンブラック分散体の製造方法＞
次に、本発明のカーボンブラック分散体の製造方法について説明する。本発明のカーボンブラック分散体は、Ｎ−メチル−２−ピロリドンが該分散体の２０重量％〜６０重量％、かつ、フッ化ビニリデン系ポリマーの重量がカーボンブラックの重量以下で、カーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンとを混練することにより製造する。Ｎ−メチル−２−ピロリドンが分散体の２０重量％未満、もしくは６０重量％より多い場合、混練によるカーボンブラックおよびフッ化ビニリデン系ポリマーの混合、分散の効率が低下する傾向が見られた。また、フッ化ビニリデン系ポリマーの重量がカーボンブラックの重量よりも多い場合、混練によるカーボンブラックおよびフッ化ビニリデン系ポリマーの混合、分散の効率が低下するだけでなく、後述する電極用合材ペーストの組成の自由度が狭まる場合がある。
<Method for producing carbon black dispersion>
Next, a method for producing the carbon black dispersion of the present invention will be described. In the carbon black dispersion of the present invention, N-methyl-2-pyrrolidone is 20% by weight to 60% by weight of the dispersion, and the weight of the vinylidene fluoride polymer is not more than the weight of the carbon black. It is produced by kneading a vinylidene fluoride polymer and N-methyl-2-pyrrolidone. When N-methyl-2-pyrrolidone was less than 20% by weight or more than 60% by weight of the dispersion, the mixing and dispersion efficiency of carbon black and vinylidene fluoride polymer by kneading tended to decrease. Further, when the weight of the vinylidene fluoride polymer is larger than the weight of the carbon black, not only does the efficiency of mixing and dispersion of the carbon black and the vinylidene fluoride polymer by kneading decrease, but also the electrode mixture paste described later In some cases, the degree of freedom of composition is narrowed.
カーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンとを混練するための装置としては、例えば、ディスパー、ホモミキサー、フェンシェルミキサー、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」、プライミクス社「フィルミックス」等）類、ペイントコンディショナー（レッドデビル社製）、ニーダー、ローラーミル、石臼式ミル、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）、クレアＳＳ−５（エム・テクニック社製）、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機、エクストルーダー類、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。 Examples of the apparatus for kneading carbon black, vinylidene fluoride polymer and N-methyl-2-pyrrolidone include mixers such as dispersers, homomixers, fen shell mixers, planetary mixers, and homogenizers (M Technique). "Clairemix", "Primics" Philmix, etc.), paint conditioner (Red Devil), kneader, roller mill, stone mill, hybridizer (Nara Machinery Co., Ltd.), Mechano Micros ( Nara Machinery Co., Ltd.), Claire SS-5 (M Technique Co., Ltd.), Mechano Fusion System AMS (Hosokawa Micron Co., Ltd.) and other medialess dispersers, extruders, roll mills, etc. It is not limited.
中でも、２本ロールミルが特に好適に用いられる。本発明の条件では２本ロールミルで混練した場合が最も効率良くカーボンブラックおよびフッ化ビニリデン系ポリマーを分散安定化できるため、得られたカーボンブラック分散体を使用して後述する電極用合材ペーストを調製した際に、同一組成での粘度が他の装置を使用した場合よりも低くなる傾向が見られた。それにより、塗工適正粘度とするために必要なＮ−メチル−２−ピロリドンの量が少なくて済むため、塗工後の乾燥時間短縮や、乾燥に要するエネルギーコストを削減することができると考えられる。 Among these, a two-roll mill is particularly preferably used. Under the conditions of the present invention, the carbon black and the vinylidene fluoride polymer can be most stably dispersed and stabilized when kneaded by a two-roll mill. Therefore, the electrode mixture paste described later is prepared using the obtained carbon black dispersion. When prepared, the viscosity with the same composition tended to be lower than when other devices were used. As a result, the amount of N-methyl-2-pyrrolidone required to achieve the proper coating viscosity can be reduced, so that the drying time after coating can be shortened and the energy cost required for drying can be reduced. It is done.
カーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンの２本ロールミルによる混練処理について説明する。本発明における２本ロールミルによる混練処理は、２本ロールミルによるせん断力を利用してカーボンブラックの凝集体を解砕しつつ、フッ化ビニリデン系ポリマーをＮ−メチル−２−ピロリドンに分散及び／または溶解させるものである。混練処理を行うときには、まずカーボンブラックと、カーボンブラック１００重量部に対し５重量部〜１００重量部、好ましくは１０重量部〜５０重量部のフッ化ビニリデン系ポリマーと、全重量の２０重量％〜６０重量％、好ましくは３０重量％〜５０重量％のＮ−メチル−２−ピロリドンとを、常温もしくは加熱下で混合し、均質な混合物を作る。 A kneading process using a two-roll mill of carbon black, a vinylidene fluoride polymer, and N-methyl-2-pyrrolidone will be described. In the kneading treatment by the two-roll mill in the present invention, the vinylidene fluoride polymer is dispersed and / or dispersed in the N-methyl-2-pyrrolidone while pulverizing the carbon black aggregate using the shear force of the two-roll mill. It is to be dissolved. When the kneading treatment is performed, first, carbon black, 5 to 100 parts by weight, preferably 10 to 50 parts by weight of vinylidene fluoride polymer with respect to 100 parts by weight of carbon black, and 20% by weight to the total weight. 60% by weight, preferably 30% to 50% by weight of N-methyl-2-pyrrolidone is mixed at room temperature or under heating to make a homogeneous mixture.
得られたカーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンの混合物を、加熱温度４０〜２００℃、回転速度を１０〜５０ｒｐｍとした２本ロールにて複数回混練処理し、断片状もしくはシート状の混練物を得る。混練回数は、希望する混練度に応じて任意に設定できる。得られた混練物がシート状の場合は、粉砕して粉状または断片状とした後に、次の工程に使用するのが好ましい。シート状の混練物を粉砕する方法としては、通常の粉砕機を用いればよく、特に限定されないが、金属コンタミ等を考慮し、フッ素樹脂コーティングやセラミック溶射処理などを施された粉砕機を用いるのが好ましい。 The obtained carbon black, vinylidene fluoride polymer, and N-methyl-2-pyrrolidone mixture were kneaded multiple times with two rolls at a heating temperature of 40 to 200 ° C. and a rotation speed of 10 to 50 rpm, and fragments were obtained. Or a sheet-like kneaded product is obtained. The number of kneading can be arbitrarily set according to the desired degree of kneading. When the obtained kneaded material is in the form of a sheet, it is preferably used in the next step after being pulverized into powder or fragments. The method for pulverizing the sheet-like kneaded material may be an ordinary pulverizer, and is not particularly limited. In consideration of metal contamination, etc., a pulverizer that has been subjected to fluororesin coating or ceramic spraying treatment is used. Is preferred.
得られた混練物は、そのまま後述する電極用合材ペーストの調製に用いても良いし、Ｎ−メチル−２−ピロリドン中に溶解及び／または分散してから電極用合材ペーストの調製に用いても良い。Ｎ−メチル−２−ピロリドン中に溶解及び／または分散するための装置としては特に限定されるものではなく、一般的なミキサー類、ホモジナイザー類などを使用できる。Ｎ−メチル−２−ピロリドン中に溶解及び／または分散する場合、金属異物等のコンタミを除く工程を入れることが好ましい。金属異物等を除去することは電池の短絡を防ぐために非常に重要となる。金属異物等を除く方法としては、磁石による除鉄や、ろ過、遠心分離等の方法が挙げられる。 The obtained kneaded product may be used as it is for preparing an electrode mixture paste as described later, or used for preparing an electrode mixture paste after being dissolved and / or dispersed in N-methyl-2-pyrrolidone. May be. The apparatus for dissolving and / or dispersing in N-methyl-2-pyrrolidone is not particularly limited, and general mixers, homogenizers, and the like can be used. When dissolving and / or dispersing in N-methyl-2-pyrrolidone, it is preferable to include a step of removing contaminants such as metallic foreign matter. It is very important to remove metallic foreign matters and the like in order to prevent a short circuit of the battery. Examples of methods for removing metallic foreign substances include iron removal with a magnet, filtration, and centrifugation.
＜電極用合材ペーストの製造方法＞
電極用合材ペーストは、カーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンの混練物、または該混練物をＮ−メチル−２−ピロリドン中に溶解及び／または分散したものに、正極活物質または負極活物質と、必要に応じてＮ−メチル−２−ピロリドン、フッ化ビニリデン系ポリマーを添加し、混合及び／または分散することにより製造することができる。Ｎ−メチル−２−ピロリドンの添加量は塗工適正粘度、乾燥工程条件などを鑑みて調整する。フッ化ビニリデン系ポリマーの添加量は塗工適正粘度、電極合材層の結着性や電池容量などを鑑みて調整する。また、この工程でフッ化ビニリデン系ポリマーを添加する場合は、Ｎ−メチル−２−ピロリドンに溶解したものを使用するのが好ましい。電極用合材ペーストの混合及び／または分散を行うための装置としては、特に限定されるものではなく、カーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンの混練に用いる装置として例示したものや、ビーズミルなどが挙げられる。
<Method for producing electrode mixture paste>
The electrode mixture paste is a kneaded product of carbon black, a vinylidene fluoride polymer and N-methyl-2-pyrrolidone, or a solution obtained by dissolving and / or dispersing the kneaded material in N-methyl-2-pyrrolidone. It can be produced by adding a positive electrode active material or a negative electrode active material and, if necessary, N-methyl-2-pyrrolidone or a vinylidene fluoride polymer, and mixing and / or dispersing. The amount of N-methyl-2-pyrrolidone added is adjusted in view of the appropriate coating viscosity and drying process conditions. The addition amount of the vinylidene fluoride polymer is adjusted in view of the appropriate coating viscosity, the binding property of the electrode mixture layer, the battery capacity, and the like. Moreover, when adding a vinylidene fluoride type polymer at this process, it is preferable to use what was melt | dissolved in N-methyl-2-pyrrolidone. The apparatus for mixing and / or dispersing the electrode mixture paste is not particularly limited, and is exemplified as an apparatus used for kneading carbon black, vinylidene fluoride polymer, and N-methyl-2-pyrrolidone. And bead mills.
＜電池用電極＞
電極について、使用する集電体の材質や形状は特に限定されず、材質としては、アルミニウム、銅、ニッケル、チタン、ステンレス等の金属や合金が用いられるが、特に正極材料としてはアルミニウムが、負極材料としては銅の使用が好ましい。また、形状としては、一般的には平板上の箔が用いられるが、表面を粗面化したものや、穴あき箔状のもの、およびメッシュ状のものも使用できる。
<Battery electrode>
Regarding the electrode, the material and shape of the current collector to be used are not particularly limited, and as the material, metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel are used. In particular, as the positive electrode material, aluminum is used as the negative electrode. The material is preferably copper. As the shape, a flat plate foil is generally used, but a roughened surface, a perforated foil shape, and a mesh shape can also be used.
集電体上に電極下地層を形成する方法としては、本発明におけるカーボンブラックとフッ化ビニリデン系ポリマーとＮ−メチル−２−ピロリドンの混練物をＮ−メチル−２−ピロリドン中に溶解及び／または分散したものを電極集電体に塗布、乾燥する方法が挙げられる。電極下地層の膜厚としては、導電性および密着性が保たれる範囲であれば特に制限されないが、一般的には０．０５μｍ以上、２０μｍ以下であり、好ましくは０．１μｍ以上、１０μｍ以下である。 As a method for forming an electrode underlayer on a current collector, a kneaded product of carbon black, vinylidene fluoride polymer and N-methyl-2-pyrrolidone in the present invention is dissolved in N-methyl-2-pyrrolidone and / or Alternatively, a method in which a dispersed material is applied to an electrode collector and dried. The film thickness of the electrode underlayer is not particularly limited as long as the conductivity and adhesion are maintained, but is generally 0.05 μm or more and 20 μm or less, preferably 0.1 μm or more and 10 μm or less. It is.
集電体上に電極合材層を形成する方法としては、集電体上に前述の電極合材ペーストを直接塗布し乾燥する方法、および集電体上に電極下地層を形成した後に電極合材ペーストを塗布し乾燥する方法などが挙げられる。また、電極下地層の上に電極合材層を形成する場合、集電体上に電極下地ペーストを塗布した後、湿潤状態のうちに電極合材ペーストを重ねて塗布し、乾燥を行っても良い。電極合材層の厚みとしては、一般的には１μｍ以上、５００μｍ以下であり、好ましくは１０μｍ以上、３００μｍ以下である。 The electrode mixture layer is formed on the current collector by directly applying the electrode mixture paste on the current collector and drying the electrode mixture layer, and after forming the electrode base layer on the current collector. The method of apply | coating material paste and drying is mentioned. In addition, when the electrode mixture layer is formed on the electrode foundation layer, after applying the electrode foundation paste on the current collector, the electrode mixture paste may be applied in a wet state and then dried. good. The thickness of the electrode mixture layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more and 300 μm or less.
塗布方法については、特に制限はなく公知の方法を用いることができる。具体的には、ダイコーティング法、ディップコーティング法、ロールコーティング法、ドクターコーティング法、スプレーコティング法、グラビアコーティング法、スクリーン印刷法、静電塗装法等が挙げられる。また、塗布後に平版プレスやカレンダーロール等による圧延処理を行っても良い。 There is no restriction | limiting in particular about the coating method, A well-known method can be used. Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method. Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application | coating.
＜リチウム二次電池＞
最後に、本発明の製造方法による分散体または合材ペーストを用いたリチウムイオン二次電池について説明する。リチウムイオン二次電池は、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。本発明のリチウムイオン二次電池は、正極および負極の少なくとも一方に、前述の電極を使用して製造することができる。
<Lithium secondary battery>
Finally, a lithium ion secondary battery using a dispersion or a composite paste according to the production method of the present invention will be described. The lithium ion secondary battery includes a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium. The lithium ion secondary battery of this invention can be manufactured using the above-mentioned electrode for at least one of a positive electrode and a negative electrode.
本発明のリチウム二次電池を構成する電解液としては、リチウムを含んだ電解質を非水系の溶剤に溶解したものを用いる。電解質としては、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、ＬｉＣ４Ｆ９ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ、ＬｉＩ、ＬｉＢｒ、ＬｉＣｌ、ＬｉＡｌＣｌ、ＬｉＨＦ２、ＬｉＳＣＮ、ＬｉＢＰｈ４等が挙げられるがこれらに限定されない。 As the electrolytic solution constituting the lithium secondary battery of the present invention, an electrolyte containing lithium is dissolved in a non-aqueous solvent. As the electrolyte, LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C , LiI, LiBr, LiCl, LiAlCl, LiHF 2 , LiSCN, LiBPh 4 and the like, but are not limited thereto.
非水系の溶剤としては特に限定はされないが、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート等のカーボネート類、γ−ブチロラクトン、γ−バレロラクトン、γ−オクタノイックラクトン等のラクトン類、テトラヒドロフラン、２−メチルテトラヒドロフラン、１，３−ジオキソラン、４−メチル−１，３−ジオキソラン、１，２−メトキシエタン、１，２−エトキシエタン、１，２−ジブトキシエタン等のグライム類、メチルフォルメート、メチルアセテート、メチルプロピオネート等のエステル類、ジメチルスルホキシド、スルホラン等のスルホキシド類、アセトニトリル等のニトリル類、が挙げられる。またこれらの溶剤は、それぞれ単独で使用しても良いが、２種以上を混合して使用しても良い。 The non-aqueous solvent is not particularly limited, but carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate, γ-butyrolactone, γ-valerolactone, and γ-octanoic lactone. Lactones such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, 1,2-dibutoxyethane, etc. Glymes, esters such as methyl formate, methyl acetate and methyl propionate, sulfoxides such as dimethyl sulfoxide and sulfolane, and nitriles such as acetonitrile. These solvents may be used alone or in combination of two or more.
更に上記電解液を、ポリマーマトリクスに保持しゲル状とした高分子電解質とすることもできる。ポリマーマトリクスとしては、ポリアルキレンオキシドセグメントを有するアクリレート系樹脂、ポリアルキレンオキシドセグメントを有するポリホスファゼン系樹脂、ポリアルキレンオキシドセグメントを有するポリシロキサン等が挙げられるがこれらに限定されない。 Furthermore, the electrolyte solution may be a gelled polymer electrolyte held in a polymer matrix. Examples of the polymer matrix include, but are not limited to, an acrylate resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, a polysiloxane having a polyalkylene oxide segment, and the like.
本発明の組成物を用いたリチウム二次電池の構造については特に限定されないが、通常、正極および負極と、必要に応じて設けられるセパレーターとから構成され、ペーパー型、円筒型、ボタン型、積層型など、使用する目的に応じた種々の形状とすることができる。 The structure of the lithium secondary battery using the composition of the present invention is not particularly limited, but it is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary. Paper type, cylindrical type, button type, laminated Various shapes can be formed according to the purpose of use, such as a mold.
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、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。また、以下Ｎ−メチル−２−ピロリドンをＮＭＰと略記する。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example, unless the summary is exceeded. In this example, “part” represents “part by weight” and “%” represents “% by weight”. Hereinafter, N-methyl-2-pyrrolidone is abbreviated as NMP.
実施例及び比較例で使用したカーボンブラック、フッ化ビニリデン系ポリマー及びその溶液、活物質を以下に示す。 The carbon black, the vinylidene fluoride polymer used in Examples and Comparative Examples, solutions thereof, and active materials are shown below.
＜カーボンブラック＞
・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、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、一次粒子径３５ｎｍ、比表面積６９ｍ２／ｇ、以下粉状品と略記する。
・Ｓｕｐｅｒ−Ｐ Ｌｉ（ＴＩＭＣＡＬ社製）：ファーネスブラック、一次粒子径４０ｎｍ、比表面積６２ｍ2／ｇ。
・ＥＣ−３００Ｊ（アクゾ社製）：ケッチェンブラック、一次粒子径４０ｎｍ、比表面積８００ｍ2／ｇ。
<Carbon black>
Denka black HS-100 (manufactured by Denki Kagaku Kogyo): acetylene black, primary particle diameter 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, primary particle diameter 35 nm, specific surface area 69 m 2 / g, hereinafter abbreviated as powdery product.
Super-P Li (manufactured by TIMCAL): furnace black, primary particle size 40 nm, specific surface area 62 m 2 / g.
EC-300J (manufactured by Akzo): Ketjen black, primary particle size 40 nm, specific surface area 800 m 2 / g.
＜フッ化ビニリデン系ポリマー及びその溶液＞
・ＫＦポリマーＷ＃１１００（クレハ社製）：ポリフッ化ビニリデン、重量平均分子量約２８万、以下Ｗ＃１１００と略記する。
・ＫＦポリマーＷ＃７３００（クレハ社製）：ポリフッ化ビニリデン、重量平均分子量約１００万、以下Ｗ＃７３００と略記する。
・ＫＦポリマーＷ＃９３００（クレハ社製）：ポリフッ化ビニリデンとヘキサフルオロプロピレンのコポリマー、重量平均分子量約１００万、以下Ｗ＃９３００と略記する。
・ＫＦポリマーＬ＃１１２０（クレハ社製）：Ｗ＃１１００の１２重量％ＮＭＰ溶液、以下Ｌ＃１１２０と略記する。
・ＫＦポリマーＬ＃７３０５（クレハ社製）：Ｗ＃７３００の５重量％ＮＭＰ溶液、以下Ｌ＃７３０５と略記する。
・ＫＦポリマーＬ＃９３０５（クレハ社製）：Ｗ＃９３００の５重量％ＮＭＰ溶液、以下Ｌ＃９３０５と略記する。
<Vinylidene fluoride polymer and its solution>
KF polymer W # 1100 (manufactured by Kureha): polyvinylidene fluoride, weight average molecular weight of about 280,000, hereinafter abbreviated as W # 1100.
KF polymer W # 7300 (manufactured by Kureha): polyvinylidene fluoride, weight average molecular weight of about 1 million, hereinafter abbreviated as W # 7300.
KF polymer W # 9300 (manufactured by Kureha): copolymer of polyvinylidene fluoride and hexafluoropropylene, weight average molecular weight of about 1 million, hereinafter abbreviated as W # 9300.
KF polymer L # 1120 (manufactured by Kureha): 12 wt% NMP solution of W # 1100, hereinafter abbreviated as L # 1120.
KF polymer L # 7305 (manufactured by Kureha): 5% by weight NMP solution of W # 7300, hereinafter abbreviated as L # 7305.
KF polymer L # 9305 (manufactured by Kureha): 5% by weight NMP solution of W # 9300, hereinafter abbreviated as L # 9305.
＜活物質＞
・ＨＬＣ−２２（本荘ケミカル社製）：正極用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）：負極用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 Co.): active material for negative electrode mesophase carbon (MFC), average particle diameter of 5 to 7 μm, specific surface area of 4 m 2 / g, hereinafter abbreviated as MFC.
＜カーボンブラック分散体の調製＞
［実施例１〜実施例５］
表１に示す組成に従い、各種カーボンブラックと各種フッ化ビニリデン系ポリマーとＮＭＰとを室温下で混合し、均質な湿潤混合物を得た。この湿潤混合物を１００℃に加温した２本ロールで繰り返し混練処理し、各種カーボンブラック分散体を得た。その後、カーボンブラック分散体を粉砕し、１４０℃の熱風オーブンで１時間乾燥したときの乾燥前後の重量差から不揮発分を求めた。さらに、ＮＭＰを用いて希釈し、動的光散乱方式の粒度分布計（日機装社製「マイクロトラックＵＰＡ」）を用いて分散粒径（Ｄ５０の値）を測定した。評価結果を表１に示した。
<Preparation of carbon black dispersion>
[Example 1 to Example 5]
According to the composition shown in Table 1, various carbon blacks, various vinylidene fluoride polymers and NMP were mixed at room temperature to obtain a homogeneous wet mixture. This wet mixture was repeatedly kneaded with two rolls heated to 100 ° C. to obtain various carbon black dispersions. Thereafter, the carbon black dispersion was pulverized and the nonvolatile content was determined from the weight difference before and after drying when dried in a hot air oven at 140 ° C. for 1 hour. Further, the sample was diluted with NMP, and the dispersed particle size (D50 value) was measured using a dynamic light scattering particle size distribution meter (“MICROTRACK UPA” manufactured by Nikkiso Co., Ltd.). The evaluation results are shown in Table 1.
［実施例６］
表１に示す組成に従い、ＨＳ−１００とＬ＃１１２０とを２軸エクストルーダ（栗本鉄工所社製）用いて混練処理し、カーボンブラック分散体を得た。その後、１４０℃の熱風オーブンで１時間乾燥したときの乾燥前後の重量差から不揮発分を求めた。さらに、ＮＭＰを用いて希釈し、動的光散乱方式の粒度分布計（日機装社製「マイクロトラックＵＰＡ」）を用いて分散粒径（Ｄ５０の値）を測定した。評価結果を表１に示した。
[Example 6]
According to the composition shown in Table 1, HS-100 and L # 1120 were kneaded using a biaxial extruder (manufactured by Kurimoto Iron Works Co., Ltd.) to obtain a carbon black dispersion. Then, the non-volatile content was calculated | required from the weight difference before and behind drying when it dried with a 140 degreeC hot-air oven for 1 hour. Further, the sample was diluted with NMP, and the dispersed particle size (D50 value) was measured using a dynamic light scattering particle size distribution meter (“MICROTRACK UPA” manufactured by Nikkiso Co., Ltd.). The evaluation results are shown in Table 1.
［比較例１］
表１に示す組成に従い、粒状品とＬ＃７３０５とをプラネタリーミキサー（プライミクス社製）を用いて混練処理し、カーボンブラック分散体を得た。その後、１４０℃の熱風オーブンで１時間乾燥したときの乾燥前後の重量差から不揮発分を求めた。さらに、ＮＭＰを用いて希釈し、動的光散乱方式の粒度分布計（日機装社製「マイクロトラックＵＰＡ」）を用いて分散粒径（Ｄ５０の値）を測定した。評価結果を表１に示した。
[Comparative Example 1]
In accordance with the composition shown in Table 1, the granular product and L # 7305 were kneaded using a planetary mixer (manufactured by Primex) to obtain a carbon black dispersion. Then, the non-volatile content was calculated | required from the weight difference before and behind drying when it dried with a 140 degreeC hot-air oven for 1 hour. Further, the sample was diluted with NMP, and the dispersed particle size (D50 value) was measured using a dynamic light scattering particle size distribution meter (“MICROTRACK UPA” manufactured by Nikkiso Co., Ltd.). The evaluation results are shown in Table 1.
［比較例２］
混練処理に使用する装置をフィルミックス（プライミクス社製）と代える他は比較例１と同様にしてカーボンブラック分散体を得た。評価も同様に行った。評価結果を表１に示した。
[Comparative Example 2]
A carbon black dispersion was obtained in the same manner as in Comparative Example 1 except that the apparatus used for the kneading treatment was replaced with Fillmix (manufactured by Primex). Evaluation was performed in the same manner. The evaluation results are shown in Table 1.
［比較例３］
使用するフッ化ビニリデン系ポリマー溶液をＬ＃９３０５とし、混練処理に使用する装置を２軸エクストルーダ（栗本鉄工所社製）と代える他は比較例１と同様にしてカーボンブラック分散体を得た。評価も同様に行った。評価結果を表１に示した。
[Comparative Example 3]
A carbon black dispersion was obtained in the same manner as in Comparative Example 1 except that the vinylidene fluoride polymer solution used was L # 9305 and the apparatus used for the kneading process was replaced with a biaxial extruder (manufactured by Kurimoto Iron Works). Evaluation was performed in the same manner. The evaluation results are shown in Table 1.
表中、Ｌ＃１１２０、Ｌ＃７３０５、Ｌ＃９３０５に含まれるＮＭＰの量を括弧書きで示した。 In the table, the amount of NMP included in L # 1120, L # 7305, and L # 9305 is shown in parentheses.
表１より、実施例の分散体は比較例の分散体に比べて分散粒度が小さいことが分かる。 From Table 1, it can be seen that the dispersion of the example has a smaller dispersion particle size than the dispersion of the comparative example.
［実施例７、実施例８］
表２に示す組成に従い、実施例２および実施例５のカーボンブラック分散体とＮＭＰとをディスパーで混合し、各種カーボンブラック分散体を得た。得られた分散体の分散粒径は、動的光散乱方式の粒度分布計（日機装社製「マイクロトラックＵＰＡ」）を用いて分散粒径（Ｄ５０の値）を測定した。また、Ｂ型粘度計（東機産業社製「ＢＬ」）を用いて、２５℃、６０ｒｐｍで粘度の測定を行った。評価結果を表２に示した。
[Example 7, Example 8]
According to the composition shown in Table 2, the carbon black dispersions of Example 2 and Example 5 and NMP were mixed with a disper to obtain various carbon black dispersions. The dispersed particle size of the obtained dispersion was measured using a dynamic light scattering particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.). Moreover, the viscosity was measured at 25 ° C. and 60 rpm using a B-type viscometer (“BL” manufactured by Toki Sangyo Co., Ltd.). The evaluation results are shown in Table 2.
［比較例４〜比較例６］
表２に示す組成に従い、比較例１〜比較例３のカーボンブラック分散体とＮＭＰとをディスパーで混合したが、分散体はいずれも著しく凝集していた。得られた分散体の分散粒径は、動的光散乱方式の粒度分布計（日機装社製「マイクロトラックＵＰＡ」）を用いて分散粒径（Ｄ５０の値）を測定した。また、Ｂ型粘度計（東機産業社製「ＢＬ」）を用いて、２５℃、６０ｒｐｍで粘度の測定を行った。評価結果を表２に示した。
[Comparative Examples 4 to 6]
According to the composition shown in Table 2, the carbon black dispersions of Comparative Examples 1 to 3 and NMP were mixed with a disper, but all of the dispersions were remarkably aggregated. The dispersed particle size of the obtained dispersion was measured using a dynamic light scattering particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.). Moreover, the viscosity was measured at 25 ° C. and 60 rpm using a B-type viscometer (“BL” manufactured by Toki Sangyo Co., Ltd.). The evaluation results are shown in Table 2.
表中、Ｌ＃７３０５、Ｌ＃９３０５に含まれるＮＭＰの量を含めた、分散体中のＮＭＰの量を括弧書きで示した。 In the table, the amount of NMP in the dispersion including the amount of NMP contained in L # 7305 and L # 9305 is shown in parentheses.
表２より、実施例の分散体は比較例の分散体に比べて、同組成で低粘度かつ分散粒度が小さいことが分かる。 From Table 2, it can be seen that the dispersions of the examples have the same composition and a low viscosity and a small dispersion particle size compared to the dispersions of the comparative examples.
＜電池電極用合材ペーストの調製＞
実施例、比較例で得られた電池電極用合材ペーストの評価は、不揮発分、粘度の測定と、ＰＥＴフィルム上にドクターブレードを用いて塗布した後、乾燥し、塗膜の表面抵抗と外観により行った。不揮発分は１４０℃の熱風オーブンで１時間乾燥したときの乾燥前後の重量差からを求めた。粘度の測定はＢ型粘度計（東機産業社製「ＢＬ」）を用いて、２５℃、６０ｒｐｍでを行った。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）を用いた（ＪＩＳＫ７１９４に準ず）。塗膜外観は目視で○：問題なし、×：粗粒の筋引きあり、とした。
<Preparation of paste for battery electrode>
The evaluation of the paste for battery electrodes obtained in Examples and Comparative Examples was carried out by measuring the non-volatile content and viscosity, applying the PET film on a PET film using a doctor blade, and then drying, and then coating surface resistance and appearance It went by. The nonvolatile content was determined from the weight difference before and after drying in a hot air oven at 140 ° C. for 1 hour. The viscosity was measured at 25 ° C. and 60 rpm using a B-type viscometer (“BL” manufactured by Toki Sangyo Co., Ltd.). Loresta-GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used for measuring the surface resistance (according to JISK7194). The appearance of the coating film was visually evaluated as O: no problem, and X: coarse graining.
［実施例９〜実施例１６、比較例７〜比較例１２］
表３に示す組成に従い、ＬＣＯまたはＭＦＣと、先に実施例または比較例で調製した各種分散体、および各種フッ化ビニリデン系ポリマー溶液をディスパーにて混合し、各種電池電極用合材ペーストを得た。その際、活物質：カーボンブラック：フッ化ビニリデン系ポリマーの比率が、Ｗ＃１１００およびＬ＃１１２０を使用した場合、９０：５：５となるように、Ｗ＃７３００、Ｗ＃９３００、Ｌ＃７３０５、およびＬ＃９３０５を使用した場合、９２：５：３となるようにフッ化ビニリデン系ポリマー溶液を添加した。評価結果を表３に示した。
[Examples 9 to 16, Comparative Examples 7 to 12]
According to the composition shown in Table 3, LCO or MFC, various dispersions previously prepared in Examples or Comparative Examples, and various vinylidene fluoride polymer solutions were mixed with a disper to obtain various pastes for battery electrodes. It was. At that time, when the ratio of the active material: carbon black: vinylidene fluoride polymer is W # 1100 and L # 1120, it is 90: 5: 5, so that W # 7300, W # 9300, L # When 7305 and L # 9305 were used, the vinylidene fluoride polymer solution was added so as to be 92: 5: 3. The evaluation results are shown in Table 3.
［比較例１３、比較例１４］
表３に示す組成に従い、ＬＣＯまたはＭＦＣと、粒状品と、Ｌ＃７３０５またはＬ＃９３０５と、ＮＭＰとをディスパーにて混合し、各種電池電極用合材ペーストを得た。その際、活物質：カーボンブラック：フッ化ビニリデン系ポリマーの比率が９２：５：３となるようにフッ化ビニリデン系ポリマー溶液を添加した。評価結果を表３に示した。
[Comparative Example 13 and Comparative Example 14]
According to the composition shown in Table 3, LCO or MFC, a granular product, L # 7305 or L # 9305, and NMP were mixed with a disper to obtain various battery electrode mixture pastes. At that time, the vinylidene fluoride polymer solution was added so that the ratio of active material: carbon black: vinylidene fluoride polymer was 92: 5: 3. The evaluation results are shown in Table 3.
表中、Ｌ＃１１２０、Ｌ＃７３０５、Ｌ＃９３０５に含まれるＮＭＰの量を含めた、分散体中およい電極用合材ペースト中のＮＭＰの量を括弧書きで示した。 In the table, the amount of NMP in the electrode mixture paste good in the dispersion including the amount of NMP contained in L # 1120, L # 7305, and L # 9305 is shown in parentheses.
表３より、本発明の分散体を使用した実施例の電池電極用合材ペーストは、比較例に比べて塗膜の表面抵抗が優れていることが分かる。比較例７〜比較例１０、比較例１３、比較例１４の電極用合材ペーストを塗工したＰＥＴフィルムは粗粒に起因する筋引きが入ってしまった。また、ほぼ同一組成である実施例１５と比較例１０および比較例１１、実施例１６と比較例１２を比較すると、実施例の分散体を使用した電池電極用合材ペーストは良好な粘性で塗工に適するのに対し、比較例の分散体を使用した電池電極用合材ペーストは粘度が高く、実際の電池用電極製造ではさらにＮＭＰを添加する必要があると思われる。また、分散体を作成せず、一括で混合した比較例１３、比較例１４に関しても粘度が高く、実際の電池用電極製造ではさらにＮＭＰを添加する必要があると思われる。 From Table 3, it can be seen that the battery electrode composite paste of the example using the dispersion of the present invention is superior in surface resistance of the coating film as compared with the comparative example. The PET films coated with the electrode mixture pastes of Comparative Examples 7 to 10, Comparative Example 13, and Comparative Example 14 had striations due to coarse particles. In addition, when Example 15 and Comparative Example 10 and Comparative Example 11 and Example 16 and Comparative Example 12 having substantially the same composition were compared, the battery electrode composite paste using the dispersion of Example was applied with good viscosity. While suitable for construction, the battery electrode composite paste using the dispersion of the comparative example has a high viscosity, and it seems that NMP needs to be further added in actual battery electrode production. Moreover, the comparative example 13 and the comparative example 14 which were mixed at a time without preparing a dispersion also had a high viscosity, and it seems that it is necessary to add NMP further in actual battery electrode manufacture.
＜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１７〜実施例２２、比較例１３〜比較例１７］
先に調製した電池電極用合材（実施例９〜実施例１２、実施例１４、実施例１５、比較例７、比較例８、比較例１０、比較例１１、比較例１３）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１:１に混合した混合溶媒にＬｉＰＦ６を１Ｍの濃度で溶解させた非水電解液）を満たして二極密閉式金属セル（宝仙社製ＨＳフラットセル）を組み立てた。セルの組み立てはアルゴンガス置換したグローブボックス内で行った。
<Assembly of lithium ion secondary battery positive electrode evaluation cell>
[Examples 17 to 22, Comparative Examples 13 to 17]
The previously prepared composite materials for battery electrodes (Examples 9 to 12, Example 14, Example 15, Comparative Example 7, Comparative Example 8, Comparative Example 10, Comparative Example 11, Comparative Example 13) were collected. After applying using a doctor blade on a 20 μm thick aluminum foil to be a body, it was dried by heating at 120 ° C. under reduced pressure, and then rolled with a roller press to produce a positive electrode mixture layer having a thickness of 100 μm. . 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 (non-aqueous electrolyte solution in which LiPF 6 is dissolved at a concentration of 1 M in a mixed solvent of ethylene carbonate and diethyl carbonate in a ratio of 1: 1) is filled, and a bipolar electrode type metal cell (HS flat cell manufactured by Hosensha) ) Was assembled. 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２３、実施例２４、比較例１８〜比較例２０］
先に調製した電池電極用合材（実施例１３、実施例１６、比較例９、比較例１２、比較例１４）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１:１に混合した混合溶媒にＬｉＰＦ６を１Ｍの濃度で溶解させた非水電解液）を満たして二極密閉式金属セル（宝仙社製ＨＳフラットセル）を組み立てた。セルの組み立てはアルゴンガス置換したグローブボックス内で行った。
<Assembly of lithium ion secondary battery negative electrode evaluation cell>
[Example 23, Example 24, Comparative Example 18 to Comparative Example 20]
Using the doctor blade, the previously prepared composite material for battery electrodes (Example 13, Example 16, Comparative Example 9, Comparative Example 12, Comparative Example 14) was placed on a 20 μm thick aluminum foil serving as a current collector. After the coating, it was dried by heating at 120 ° C. under reduced pressure, and then rolled with a roller press to produce a negative electrode mixture layer having a thickness of 100 μm. 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 (non-aqueous electrolyte solution in which LiPF 6 is dissolved at a concentration of 1 M in a mixed solvent of ethylene carbonate and diethyl carbonate in a ratio of 1: 1) is filled, and a bipolar electrode type metal cell (HS flat cell manufactured by Hosensha) ) Was assembled. 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＞
作製した電池評価用セルを室温（２５℃）で、充電レート０．２Ｃ、１．０Ｃの定電流定電圧充電（上限電圧４．２Ｖ）で満充電とし、充電時と同じレートの定電流で放電下限電圧３．０Ｖまで放電を行う充放電を１サイクル（充放電間隔休止時間３０分）とし、このサイクルを合計２０サイクル行い、充放電サイクル特性評価（評価装置：北斗電工社製ＳＭ−８）を行った。また、評価後のセルを分解し、電極塗膜の外観を目視にて確認し、部分的に合材が集電体より剥がれているのが確認された場合に×とした。評価結果を表４に示した。
<Characteristic evaluation of lithium ion secondary battery positive electrode>
The produced battery evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 4.2 V) at a room temperature (25 ° C.) with a charge rate of 0.2 C and 1.0 C, and at a constant current at the same rate as during charging. Charge / discharge for discharging to a discharge lower limit voltage of 3.0V is defined as one cycle (charge / discharge interval rest time 30 minutes), and this cycle is performed for a total of 20 cycles to evaluate charge / discharge cycle characteristics (Evaluation apparatus: SM-8 manufactured by Hokuto Denko Co. ) Moreover, the cell after evaluation was decomposed | disassembled, the external appearance of the electrode coating film was confirmed visually, and it was set as x when it was confirmed that the composite material has partially peeled from the electrical power collector. The evaluation results are shown in Table 4.
表４より、本発明の電極を使用した実施例は、比較例に比べて電池容量、２０サイクル容量維持率において良好な結果が得られた。特に、混練工程に２本ロールミルを使用した実施例において、良好な評価結果が得られた。比較例１３〜比較例１５、比較例１７は評価後、集電体から合材が剥落していた。 From Table 4, the example using the electrode of the present invention showed better results in battery capacity and 20 cycle capacity maintenance rate than the comparative example. In particular, good evaluation results were obtained in Examples using a two-roll mill for the kneading step. In Comparative Examples 13 to 15 and Comparative Example 17, the composite material was peeled off from the current collector after evaluation.
＜リチウムイオン二次電池負極特性評価＞
作製した電池評価用セルを室温（２５℃）で、充電レート０．２Ｃ、１．０Ｃの定電流定電圧充電（上限電圧０．５Ｖ）で満充電とし、充電時と同じレートの定電流で電圧が１．５Ｖになるまで放電を行う充放電を１サイクル（充放電間隔休止時間３０分）とし、このサイクルを合計２０サイクル行い、充放電サイクル特性評価（評価装置：北斗電工製ＳＭ−８）を行った。また、評価後のセルを分解し、電極塗膜不良の有無を目視にて確認し、部分的に合材が集電体より剥がれているのが確認された場合に×とした。評価結果を表５に示した。
<Evaluation of lithium ion secondary battery negative electrode characteristics>
The produced battery evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 0.5 V) at a room temperature (25 ° C.) and at a charge rate of 0.2 C and 1.0 C, and at a constant current at the same rate as the charge Charging / discharging for discharging until the voltage reaches 1.5 V is defined as one cycle (charging / discharging interval rest time 30 minutes), and this cycle is performed for a total of 20 cycles to evaluate charging / discharging cycle characteristics (Evaluation apparatus: SM-8 manufactured by Hokuto Denko) ) Moreover, the cell after evaluation was decomposed | disassembled, the presence or absence of the electrode coating film defect was confirmed visually, and it was set as x when it was confirmed that the composite material has partially peeled from the electrical power collector. 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は、比較例に比べて電池容量、２０サイクル容量維持率において良好な結果が得られた。比較例１８、比較例２０は評価後、集電体から合材が剥落していた。 From Table 5, the example using the electrode of the present invention showed better results in battery capacity and 20 cycle capacity maintenance rate than the comparative example. In Comparative Examples 18 and 20, the composite material was peeled off from the current collector after evaluation.
＜リチウムイオン二次電池電極下地層評価＞
［実施例２５、実施例２６、比較例２１、比較例２２］
先に調製したカーボンブラック分散体（実施例８、比較例６）をを、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、厚さ２μｍの電極下地層を作製した。次に電極下地層上に比較例８で調整した正極合材ペースト、または比較例９で調製した負極合材ペーストを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、厚さ１００μｍの電極合材層を作製した。ロールプレス等による圧延処理は行わなかった。
<Evaluation of lithium ion secondary battery electrode underlayer>
[Example 25, Example 26, Comparative Example 21, Comparative Example 22]
The previously prepared carbon black dispersion (Example 8, Comparative Example 6) was applied onto a 20 μm thick aluminum foil serving as a current collector using a doctor blade, and then heated and dried at 120 ° C. under reduced pressure. An electrode underlayer having a thickness of 2 μm was prepared. Next, the positive electrode mixture paste prepared in Comparative Example 8 or the negative electrode mixture paste prepared in Comparative Example 9 was applied on the electrode underlayer using a doctor blade, and then heated and dried at 120 ° C. under reduced pressure to obtain a thickness. A 100 μm electrode mixture layer was produced. The rolling process by a roll press etc. was not performed.
電極下地層と正極合材層が形成された集電体（実施例２５および比較例２１）を直径９ｍｍに打ち抜き作用極とし、金属リチウム箔（厚さ０．１５ｍｍ）を対極として、作用極および対極の間に多孔質ポリプロピレンフィルムからなるセパレーター（セルガード社製＃２４００）を挿入積層し、電解液（エチレンカーボネートとジエチルカーボネートを１:１に混合した混合溶媒にＬｉＰＦ６を１Ｍの濃度で溶解させた非水電解液）を満たして二極密閉式金属セル（宝仙社製ＨＳフラットセル）を組み立てた。セルの組み立てはアルゴンガス置換したグローブボックス内で行った。 A current collector (Example 25 and Comparative Example 21) on which an electrode underlayer and a positive electrode mixture layer were formed was punched into a diameter of 9 mm as a working electrode, a metal lithium foil (thickness: 0.15 mm) as a counter electrode, A separator made of a porous polypropylene film (# 2400 made by Celgard) was inserted and laminated between the counter electrodes, and LiPF 6 was dissolved at a concentration of 1M in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed in a 1: 1 ratio. In addition, a two-pole sealed metal cell (HS flat cell manufactured by Hosensha) was assembled. The cell was assembled in a glove box substituted with argon gas.
電極下地層と負極合材層が形成された集電体（実施例２６および比較例２２）を直径９ｍｍに打ち抜き作用極とし、金属リチウム箔（厚さ０．１５ｍｍ）を対極として、作用極および対極の間に多孔質ポリプロピレンフィルムからなるセパレーター（セルガード社製＃２４００）を挿入積層し、電解液（エチレンカーボネートとジエチルカーボネートを１:１に混合した混合溶媒にＬｉＰＦ６を１Ｍの濃度で溶解させた非水電解液）を満たして二極密閉式金属セル（宝仙社製ＨＳフラットセル）を組み立てた。セルの組み立てはアルゴンガス置換したグローブボックス内で行った。 A current collector (Example 26 and Comparative Example 22) in which an electrode underlayer and a negative electrode mixture layer were formed was punched out to a diameter of 9 mm as a working electrode, a metal lithium foil (thickness 0.15 mm) as a counter electrode, A separator made of a porous polypropylene film (# 2400 made by Celgard) was inserted and laminated between the counter electrodes, and LiPF 6 was dissolved at a concentration of 1M in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed in a 1: 1 ratio. In addition, a two-pole sealed metal cell (HS flat cell manufactured by Hosensha) was assembled. The cell was assembled in a glove box substituted with argon gas.
作製した電池評価用セル（実施例２５および比較例２１）を室温（２５℃）で、充電レート０．２Ｃ、１．０Ｃの定電流定電圧充電（上限電圧４．２Ｖ）で満充電とし、充電時と同じレートの定電流で放電下限電圧３．０Ｖまで放電を行う充放電を１サイクル（充放電間隔休止時間３０分）とし、このサイクルを合計２０サイクル行い、１０サイクル後、２０サイクル後のセルを分解し、電極塗膜の外観を目視にて確認し、部分的に合材が集電体より剥がれているのが確認された場合に×とした。評価結果を表６に示した。 The produced battery evaluation cells (Example 25 and Comparative Example 21) were fully charged at room temperature (25 ° C.) with a constant current and constant voltage charge (upper limit voltage 4.2 V) at a charge rate of 0.2 C and 1.0 C. Charging / discharging which discharges to a discharge lower limit voltage of 3.0 V at a constant current at the same rate as that of charging is defined as one cycle (charging / discharging interval pause time 30 minutes), and this cycle is performed for a total of 20 cycles. The cell was disassembled, the appearance of the electrode coating film was visually confirmed, and x was marked when it was confirmed that the composite material was partially peeled from the current collector. The evaluation results are shown in Table 6.
作製した電池評価用セル（実施例２６および比較例２２）を室温（２５℃）で、充電レート０．２Ｃ、１．０Ｃの定電流定電圧充電（上限電圧４．２Ｖ）で満充電とし、充電時と同じレートの定電流で放電下限電圧３．０Ｖまで放電を行う充放電を１サイクル（充放電間隔休止時間３０分）とし、このサイクルを合計２０サイクル行い、１０サイクル後、２０サイクル後のセルを分解し、電極塗膜の外観を目視にて確認し、部分的に合材が集電体より剥がれているのが確認された場合に×とした。評価結果を表６に示した。 The produced battery evaluation cells (Example 26 and Comparative Example 22) were fully charged at room temperature (25 ° C.) with a constant current and constant voltage charge (upper limit voltage 4.2 V) at a charge rate of 0.2 C and 1.0 C. Charging / discharging which discharges to a discharge lower limit voltage of 3.0 V at a constant current at the same rate as that of charging is defined as one cycle (charging / discharging interval pause time 30 minutes), and this cycle is performed for a total of 20 cycles. The cell was disassembled, the appearance of the electrode coating film was visually confirmed, and x was marked when it was confirmed that the composite material was partially peeled from the current collector. The evaluation results are shown in Table 6.
表６より、本発明の電極下地層を設けた電極では密着性の向上が見られた。 From Table 6, the improvement of adhesiveness was seen in the electrode provided with the electrode base layer of the present invention.
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