JPWO2011055680A1 - Copper foil for lithium-ion battery current collector - Google Patents
Copper foil for lithium-ion battery current collector Download PDFInfo
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- JPWO2011055680A1 JPWO2011055680A1 JP2011539352A JP2011539352A JPWO2011055680A1 JP WO2011055680 A1 JPWO2011055680 A1 JP WO2011055680A1 JP 2011539352 A JP2011539352 A JP 2011539352A JP 2011539352 A JP2011539352 A JP 2011539352A JP WO2011055680 A1 JPWO2011055680 A1 JP WO2011055680A1
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- Prior art keywords
- copper foil
- group
- water
- compound
- ion battery
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000011889 copper foil Substances 0.000 title claims abstract description 118
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 68
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 68
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 61
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 60
- -1 azole compound Chemical class 0.000 claims abstract description 57
- 238000004381 surface treatment Methods 0.000 claims description 49
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 29
- 125000003700 epoxy group Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 125000002883 imidazolyl group Chemical group 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 125000001033 ether group Chemical group 0.000 claims description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000004846 water-soluble epoxy resin Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 48
- 230000002265 prevention Effects 0.000 abstract description 37
- 239000010410 layer Substances 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000003466 welding Methods 0.000 description 10
- 230000003301 hydrolyzing effect Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000003449 preventive effect Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
- 239000012756 surface treatment agent Substances 0.000 description 7
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000010731 rolling oil Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 239000002033 PVDF binder 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
- 150000003851 azoles Chemical class 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- HXQHRUJXQJEGER-UHFFFAOYSA-N 1-methylbenzotriazole Chemical compound C1=CC=C2N(C)N=NC2=C1 HXQHRUJXQJEGER-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- LJVNVNLFZQFJHU-UHFFFAOYSA-N 2-(2-phenylmethoxyethoxy)ethanol Chemical compound OCCOCCOCC1=CC=CC=C1 LJVNVNLFZQFJHU-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- OKQVTLCUHATGDD-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-2-ethyl-n-(2-ethylhexyl)hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1 OKQVTLCUHATGDD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
防錆性及び水濡れ性がバランス良く向上したリチウムイオン電池の集電体用銅箔を提供する。リチウムイオン電池集電体用銅箔は、銅箔表面の少なくとも一部にアゾール化合物、及び、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物を含む水溶性有機化合物の混合層が形成されている。Provided is a copper foil for a current collector of a lithium ion battery having improved rust prevention and water wettability in a well-balanced manner. The copper foil for a lithium ion battery current collector has a mixed layer of a water-soluble organic compound containing an azole compound on at least a part of the copper foil surface and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. Is formed.
Description
本発明はリチウムイオン電池集電体用銅箔に関し、とりわけ水系バインダーを使ったリチウムイオン二次電池負極集電体用銅箔に関する。 The present invention relates to a copper foil for a lithium ion battery current collector, and more particularly to a copper foil for a negative electrode current collector of a lithium ion secondary battery using an aqueous binder.
リチウムイオン電池はエネルギー密度が高く、比較的高い電圧を得ることができるという特徴を有し、ノートパソコン、ビデオカメラ、デジタルカメラ、携帯電話等の小型電子機器用に多用されている。将来、電気自動車や一般家庭の分散配置型電源といった大型機器の電源としての利用も有望視されている。 Lithium ion batteries have a feature of high energy density and a relatively high voltage, and are widely used for small electronic devices such as notebook computers, video cameras, digital cameras, and mobile phones. In the future, it is expected to be used as a power source for large equipment such as electric vehicles and distributed power sources for general households.
リチウムイオン電池の電極体は一般に、図1に示すように、正極11、セパレータ12及び負極13が幾十にも巻回又は積層されたスタック構造を有している。典型的には、正極は、アルミニウム箔でできた正極集電体とその表面に設けられたLiCoO2、LiNiO2及びLiMn2O4といったリチウム複合酸化物を材料とする正極活物質から構成され、負極は銅箔でできた負極集電体とその表面に設けられたカーボン等を材料とする負極活物質から構成される。正極同士及び負極同士は各タブ(14、15)でそれぞれ溶接される。また、正極及び負極はアルミニウムやニッケル製のタブ端子と接続されるが、これも溶接により行われる。溶接は超音波溶接により行われるのが通常である。As shown in FIG. 1, an electrode body of a lithium ion battery generally has a stack structure in which a
負極活物質には、従来、カーボンが多く使われており、これにバインダーであるポリフッ化ビニリデン(PVDF)と溶剤であるN−メチル−2−ピロリドン(NMP)を混合して銅箔表面に塗布する方法が広く用いられている。一方、電池容量の増加が求められ、これに対応して負極活物質もカーボン以外のSiやSn等の合金系が種々検討されており、さらにバインダーとして、スチレンブタジエンゴム(SBR)やアクリル系の樹脂が使用されている。これらの樹脂は、水に分散させ、さらに増粘剤を加えてスラリーを作製して銅箔表面に塗布されており、溶剤系のPVDFに対して水系バインダーと呼ばれている。 Conventionally, carbon is often used as the negative electrode active material, and this is mixed with polyvinylidene fluoride (PVDF) as a binder and N-methyl-2-pyrrolidone (NMP) as a solvent and applied to the surface of the copper foil. This method is widely used. On the other hand, there is a demand for an increase in battery capacity. Correspondingly, various types of alloys such as Si and Sn other than carbon have been studied for the negative electrode active material, and styrene butadiene rubber (SBR) or acrylic as a binder. Resin is used. These resins are dispersed in water, and a thickener is further added to prepare a slurry, which is applied to the surface of the copper foil, and is called an aqueous binder for solvent-based PVDF.
溶剤系バインダー及び水系バインダーは、一般に銅箔表面への塗工性が異なるが、これは、塗工性が銅箔表面と溶剤、あるいは水との濡れやすさに依存するためであり、水系バインダーの塗工性を改善するには、銅箔表面の水濡れ性を改善する必要がある。濡れやすさは、対象とする材料表面上に一定量の液滴を保持した場合の接触角を測定して評価する方法が広く用いられており、接触角が小さいほど濡れ性が良好となる。 Solvent-based binders and water-based binders generally have different coating properties on the copper foil surface, because this depends on the wettability between the copper foil surface and the solvent or water. In order to improve the coatability of the copper foil, it is necessary to improve the water wettability of the copper foil surface. As the wettability, a method of measuring and evaluating a contact angle when a certain amount of droplets is held on the surface of a target material is widely used. The smaller the contact angle, the better the wettability.
水濡れ性を向上させる方法としては、圧延銅箔の場合には、圧延油の除去を目的としてよく洗浄する、圧延油を揮発させる、あるいは表面への残留油分を少なくする方法が知られている。例えば、特許第2970724号では、不活性ガスまたは真空化で180℃以上で銅箔を加熱して銅箔表面上の圧延油を蒸発させる方法が記載されている。また、特許第2970727号では、最終圧延ロールの表面粗度(Ra)を1.0μm未満として材料の表面粗さを小さくし、凹部に侵入する圧延油を少なくする方法が記載されている。その他、銅箔表面を加熱して酸化皮膜層を形成する方法(例えば、特許第2928065号)、銅箔上にアゾール系誘導体含有の第一膜を形成後、さらにソルビタン系誘導体含有の第二膜を形成する方法(特許第2943898号)が記載されている。 As a method for improving water wettability, in the case of a rolled copper foil, a method of washing well for the purpose of removing the rolling oil, volatilizing the rolling oil, or reducing the residual oil content on the surface is known. . For example, Japanese Patent No. 2970724 describes a method of evaporating the rolling oil on the surface of the copper foil by heating the copper foil at 180 ° C. or higher by inert gas or evacuation. Japanese Patent No. 2970727 describes a method in which the surface roughness (Ra) of the final rolling roll is less than 1.0 μm, the surface roughness of the material is reduced, and the rolling oil entering the recess is reduced. In addition, a method of forming an oxide film layer by heating the copper foil surface (for example, Japanese Patent No. 2928065), after forming a first film containing an azole derivative on the copper foil, and further containing a second film containing a sorbitan derivative (Patent No. 2943898) is described.
また、銅箔表面の錆による劣化を防止することも重要であり、そのような防錆性を向上させる方法としては、銅箔表面をクロメート処理やシランカップリング処理する方法が知られている。シランカップリング処理は、密着性の向上効果も得られる。例えば、特開2008−184657号公報には、銅箔の少なくとも一方の面に、ニッケル、コバルト、タングステン、モリブデンのうち少なくとも一つ以上から選択された金属又はこれら金属とメタロイド金属であるリン又は、ほう素との間で形成されたバリア層を形成し、次いで形成したバリア層上に三価クロムをクロム源とするクロメート処理を施し、得られた三価クロメート皮膜上にシランカップリング処理を施すことで、密着性及び防錆性が向上したことが記載されている。 It is also important to prevent deterioration of the copper foil surface due to rust, and as a method for improving such rust prevention, a method of chromate treatment or silane coupling treatment on the copper foil surface is known. Silane coupling treatment can also improve adhesion. For example, in Japanese Patent Application Laid-Open No. 2008-184657, at least one surface of a copper foil is a metal selected from at least one of nickel, cobalt, tungsten, and molybdenum, or phosphorus that is a metalloid metal and these metals, A barrier layer formed with boron is formed, then a chromate treatment using trivalent chromium as a chromium source is performed on the formed barrier layer, and a silane coupling treatment is performed on the obtained trivalent chromate film Thus, it is described that adhesion and rust prevention properties are improved.
このように、リチウムイオン電池の集電体として使用される銅箔の水濡れ性及び防錆性向上のための技術開発が行われてきているが、これらの特性をバランス良く向上させた銅箔については、いまだ満足できるものがないのが実情である。そこで、本発明は水濡れ性及び防錆性の特性をバランス良く向上したリチウムイオン電池の集電体用銅箔を提供することを第一の課題とする。本発明はそのような銅箔を製造する方法を提供することを第二の課題とする。更に、本発明は本発明に係る銅箔を集電体として用いたリチウムイオン電池を提供することを第三の課題とする。 As described above, technical development for improving water wettability and rust prevention of a copper foil used as a current collector of a lithium ion battery has been carried out, but the copper foil has improved these characteristics in a well-balanced manner. In fact, there is still nothing to be satisfied about. Then, this invention makes it the 1st subject to provide the copper foil for the collectors of the lithium ion battery which improved the wettability and the antirust property in a good balance. This invention makes it the 2nd subject to provide the method of manufacturing such copper foil. Furthermore, this invention makes it a 3rd subject to provide the lithium ion battery which used the copper foil which concerns on this invention as a collector.
本発明者は上記課題を解決するために研究を重ねたところ、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物を塗布することで水濡れ性が改善することを確認した。しかしながら、防錆性に関して、銅に広く用いられているアゾール系化合物による表面処理と比較すると、劣っていることが確認された。そこで、更に研究を重ねたところ、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物とアゾール系表面処理剤との混合液で表面処理することにより、課題解決の糸口を見出した。詳細に検討したところ、銅箔表面を分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物とアゾール系表面処理剤との混合液で表面処理することで、それぞれの表面処理剤の濃度を単独で使用する場合よりも低い濃度で十分な防錆性の効果が得られ、また、アゾール系表面処理剤を混合することによる水濡れ性の低下が僅かであることが判明した。この効果は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物による表面処理とアゾール系表面処理剤による表面処理とをそれぞれ単独で重ねて行った(表面処理剤の重ね塗り)場合には得られないものである。すなわち、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物とアゾール系表面処理剤との混合液で表面処理することにより、従来得られなかった水濡れ性及び防錆性のバランスに優れた銅箔を提供できることを見出した。 The present inventor conducted research to solve the above problems, and confirmed that the wettability is improved by applying a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. However, it was confirmed that the anticorrosion property was inferior to the surface treatment with an azole compound widely used for copper. As a result of further research, the inventors have found a clue to solving the problem by surface treatment with a mixed solution of a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule and an azole surface treatment agent. When examined in detail, by treating the copper foil surface with a mixture of a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule and an azole-based surface treatment agent, the concentration of each surface treatment agent It has been found that a sufficient rust prevention effect can be obtained at a lower concentration than the case of using the sol alone, and that the wettability is reduced slightly by mixing the azole surface treatment agent. This effect is obtained when the surface treatment with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule and the surface treatment with an azole-based surface treatment agent are performed separately (overcoated with a surface treatment agent). Cannot be obtained. That is, by surface treatment with a mixed solution of a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule and an azole surface treatment agent, a balance of water wettability and rust prevention that has not been obtained conventionally can be achieved. It has been found that an excellent copper foil can be provided.
以上の知見を基礎として完成した本発明は一側面において、銅箔表面の少なくとも一部にアゾール化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の混合層が形成されたリチウムイオン電池集電体用銅箔である。 In one aspect, the present invention completed based on the above knowledge is lithium in which a mixed layer of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is formed on at least a part of the copper foil surface. It is copper foil for ion battery collectors.
本発明に係る銅箔は一実施形態において、XPSによる深さ方向分析でO及びNを検出し、かつC検出量がバックグラウンドレベルよりも大きい深さ範囲の平均値D0が1.0〜5.0nmである。In one embodiment, the copper foil according to the present invention detects O and N by depth direction analysis by XPS, and the average value D 0 of the depth range in which the C detection amount is larger than the background level is 1.0 to 1.0. 5.0 nm.
本発明に係る銅箔は別の一実施形態において、前記水溶性有機化合物が下記一般式(1)で表される基を含む。
本発明に係る銅箔は更に別の一実施形態において、前記Xが、水酸基、フェノキシ基、ハロゲン、有機酸エステル(RCOO)、アミノ基、アルコキシ基(RO)、アルキルメルカプト基(RS)等が挙げられるが、好ましくは、下記一般式(2)、(3)又は(4)で表される基である。
本発明に係る銅箔は更に別の一実施形態において、前記式(1)で表される基が、下記反応式(5)によりエポキシ基が活性水素を有する化合物X−Hと付加反応することで得られるものである。
本発明に係る銅箔は更に別の一実施形態において、前記反応式(5)におけるエポキシ基を有する化合物が、グリシドキシ基を有する水溶性エポキシ樹脂、又は、グリシドキシ基を有するシランカップリング剤である。 In yet another embodiment of the copper foil according to the present invention, the compound having an epoxy group in the reaction formula (5) is a water-soluble epoxy resin having a glycidoxy group or a silane coupling agent having a glycidoxy group. .
本発明に係る銅箔は更に別の一実施形態において、前記水溶性有機化合物が分子内にイミダゾール基を含む。 In yet another embodiment of the copper foil according to the present invention, the water-soluble organic compound contains an imidazole group in the molecule.
本発明に係る銅箔は更に別の一実施形態において、前記銅箔表面と前記混合層との間に、アゾール化合物又はクロメート層で構成された中間層が形成されている。 In yet another embodiment of the copper foil according to the present invention, an intermediate layer composed of an azole compound or a chromate layer is formed between the copper foil surface and the mixed layer.
本発明に係る銅箔は更に別の一実施形態において、前記アゾール化合物がベンゾトリアゾール系化合物である。 In yet another embodiment of the copper foil according to the present invention, the azole compound is a benzotriazole-based compound.
本発明に係る銅箔は更に別の一実施形態において、前記ベンゾトリアゾール系化合物が1,2,3−ベンゾトリアゾールである。 In yet another embodiment of the copper foil according to the present invention, the benzotriazole-based compound is 1,2,3-benzotriazole.
本発明に係る銅箔は更に別の一実施形態において、リチウムイオン二次電池負極集電体用である。 In yet another embodiment, the copper foil according to the present invention is for a negative electrode current collector of a lithium ion secondary battery.
本発明は別の一側面において、本発明に係る銅箔を集電体として用いたリチウムイオン電池である。 In another aspect, the present invention is a lithium ion battery using the copper foil according to the present invention as a current collector.
本発明は更に別の一側面において、銅箔表面の少なくとも一部に対し、アゾール化合物と、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液で表面処理を実施して、前記アゾール化合物及び前記水溶性有機化合物の混合層を形成する工程を含むリチウムイオン電池集電体用銅箔の製造方法である。 In yet another aspect of the present invention, at least a part of the copper foil surface is subjected to surface treatment with a mixed solution of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. A method for producing a copper foil for a lithium ion battery current collector, comprising a step of forming a mixed layer of the azole compound and the water-soluble organic compound.
本発明に係るリチウムイオン電池集電体用銅箔の製造方法は別の一実施形態において、前記混合液が、アゾール化合物を0.01〜0.25g/L、及び、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物を0.5〜20g/Lで含む。 In another embodiment of the method for producing a copper foil for a lithium ion battery current collector according to the present invention, the mixed solution contains 0.01 to 0.25 g / L of an azole compound, and hydroxyl groups and wires in the molecule. A water-soluble organic compound having a chain ether bond is contained at 0.5 to 20 g / L.
本発明に係る銅箔によれば、防錆性及び水濡れ性がバランス良く向上する。そのため、リチウムイオン電池の集電体として好適に使用することができる。 According to the copper foil which concerns on this invention, rust prevention property and water wettability improve with sufficient balance. Therefore, it can be suitably used as a current collector for a lithium ion battery.
1.銅箔基材
本発明において、銅箔は電解銅箔及び圧延銅箔のいずれでもよい。また、「銅箔」には銅合金箔も含まれるものとする。銅箔の材料としては、特に制限はなく、用途や要求特性に応じて適宜選択すればよい。例えば、限定的ではないが、圧延銅箔の場合、高純度の銅(無酸素銅やタフピッチ銅等)の他、Sn入り銅、Ag入り銅、Ni、Si等を添加したCu−Ni−Si系銅合金、Cr、Zr等を添加したCu−Cr−Zr系銅合金のような銅合金が挙げられる。1. Copper foil base material In this invention, any of an electrolytic copper foil and a rolled copper foil may be sufficient as copper foil. The “copper foil” includes a copper alloy foil. There is no restriction | limiting in particular as a material of copper foil, What is necessary is just to select suitably according to a use or a required characteristic. For example, although not limited, in the case of a rolled copper foil, Cu-Ni-Si added with Sn-containing copper, Ag-containing copper, Ni, Si, etc., in addition to high-purity copper (oxygen-free copper, tough pitch copper, etc.) And copper alloys such as Cu-Cr-Zr-based copper alloys to which Cr-based copper alloys, Cr, Zr and the like are added.
銅箔の厚みは特に制限はなく、要求特性に応じて適宜選択すればよい。一般的には1〜100μmであるが、リチウム二次電池負極の集電体として使用する場合、銅箔を薄肉化した方がより高容量の電池を得ることができる。そのような観点から、典型的には2〜50μm、より典型的には5〜20μm程度である。 There is no restriction | limiting in particular in the thickness of copper foil, What is necessary is just to select suitably according to a required characteristic. Generally, the thickness is 1 to 100 μm, but when used as a current collector for a negative electrode of a lithium secondary battery, a battery having a higher capacity can be obtained by thinning the copper foil. From such a viewpoint, it is typically 2 to 50 μm, more typically about 5 to 20 μm.
2.表面処理
表面処理は、アゾール系化合物と分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液を用いて行う。表面処理は、銅箔の上下面のうち負極活物質との密着性が要求される少なくとも一面に混合液を浸漬、塗布及び噴霧などによって接触させ、その後、乾燥することでアゾール系化合物及び水溶性エポキシ樹脂を銅箔表面の銅と反応させ、銅箔表面に固定することで行う。2. Surface Treatment The surface treatment is performed using a mixed solution of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. In the surface treatment, at least one surface of the upper and lower surfaces of the copper foil that requires adhesion with the negative electrode active material is contacted by dipping, coating, spraying, etc., and then dried to dry the azole compound and water-soluble The epoxy resin is reacted with copper on the surface of the copper foil and fixed on the surface of the copper foil.
本発明では、アゾール系化合物の防錆性を利用し、それと分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合層によって負極活物質への防錆性及び水濡れ性をバランス良く向上させている。このような点から、アゾール系化合物としては、特に良好な防錆性を有することが一般的に知られているベンゾトリアゾール系化合物が好ましい。また、ベンゾトリアゾール系化合物としては、限定されず、上述の本発明の目的からはどのようなものであってもよい。ベンゾトリアゾール系化合物としては、例えば、1,2,3−ベンゾトリアゾール、1−メチルベンゾトリアゾール、カルボキシベンゾトリアゾール、1−[N,N−ビス(2−エチルヘキシル)アミノメチル]ベンゾトリアゾール、トリルトリアゾール、ナフトトリアゾール、5−ニトロベンゾトリアゾール、及び、フェナジノトリアゾール等のベンゾトリアゾール系化合物が挙げられる。 In the present invention, the anti-rust property of the azole compound is utilized, and the anti-rust property and water wettability to the negative electrode active material are obtained by a mixed layer of the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. The balance is improved. From such a point, as the azole compound, a benzotriazole compound generally known to have particularly good rust prevention properties is preferable. Moreover, it does not limit as a benzotriazole type compound, What kind of thing may be sufficient from the objective of the above-mentioned this invention. Examples of the benzotriazole-based compound include 1,2,3-benzotriazole, 1-methylbenzotriazole, carboxybenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, tolyltriazole, Examples thereof include benzotriazole compounds such as naphthotriazole, 5-nitrobenzotriazole, and phenazinotriazole.
分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物は、下記一般式(1)で表される基を含んでいる。
上記列挙したXのうち、代表的なものを下記一般式(2)、(3)及び(4)に示す。
また、式(1)で表される基は、下記反応式(5)によりエポキシ基が活性水素を有する化合物X−Hと付加反応することで得られるものであってもよい。
上記水溶性有機化合物は、さらにはエチレングリコールモノフェニルエーテル、ジエチレングリコールモノフェニルエーテル、ジエチレングリコールモノベンジルエーテル、プロピレングリコールモノフェニルエーテルなどのグリコールエーテル類、及び、下記一般式(A)〜(G)で示されるエポキシ基をもつ化合物が、加水分解することで水酸基が付与される、又は、アミン化合物と付加反応することにより得られる、又は、イミダゾール化合物と付加反応することにより得られる化合物である。 The water-soluble organic compound is further represented by glycol ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, propylene glycol monophenyl ether, and the following general formulas (A) to (G). The compound having an epoxy group is a compound to which a hydroxyl group is imparted by hydrolysis, or obtained by addition reaction with an amine compound, or obtained by addition reaction with an imidazole compound.
水濡れ性の改善に着目した場合、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物で表面処理をすることに効果があることは考えられるが、防錆性と超音波溶接性への影響は不明である。また、銅箔の防錆処理にはアゾール系化合物が広く用いられているが、アゾール系化合物で表面処理をすると水濡れ性が低下する場合が多く、水濡れ性と防錆性を両立させることは困難である。水濡れ性と防錆性を両立させる方法として、一方の表面処理後に他方の表面処理をする、すなわち上塗り、あるいは重ね塗りが考えられるが、アゾール系化合物の表面処理後に分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物による表面処理をした場合は防錆性が低下し、また、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物による表面処理後にアゾール系化合物の表面処理をした場合は、水濡れ性が低下してしまい、水濡れ性と防錆性とを両立させることはできない。そこで、本発明では、アゾール系化合物と分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液で一度に表面処理することで、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物で得られる水濡れ性とアゾール系化合物による表面処理で得られる防錆性とを両立させることとした。 When focusing on improving water wettability, it may be effective for surface treatment with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, but rust prevention and ultrasonic weldability. The impact on is unknown. In addition, azole compounds are widely used for rust prevention treatment of copper foil, but surface treatment with azole compounds often reduces water wettability, making water wettability and rust preventive compatible. It is difficult. As a method to achieve both water wettability and rust prevention, the other surface treatment can be applied after one surface treatment, that is, overcoating or overcoating can be considered. When surface treatment is performed with a water-soluble organic compound having an ether bond, the rust resistance is reduced, and the surface of the azole compound after the surface treatment with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. When the treatment is performed, the water wettability is lowered, and the water wettability and the rust preventive property cannot be made compatible. Therefore, in the present invention, the surface treatment is performed at once with a mixed solution of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, whereby the hydroxyl group and the linear ether bond are formed in the molecule. The water wettability obtained with the water-soluble organic compound possessed and the rust prevention obtained by the surface treatment with the azole compound were made compatible.
さらに、アゾール系化合物と分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液で表面処理を行う場合には、それぞれ単独で使用する場合よりも低濃度で十分な効果が得られる。すなわち、該表面処理により形成された銅箔表面の混合層の平均厚みが薄くても十分な防錆性及び水濡れ性が得られることを見出した。また、混合層の平均厚みを薄くすれば、超音波溶接性が良好となるため、優れた防錆性、水濡れ性及び超音波溶接性をバランス良く備えることができる。 Furthermore, when surface treatment is performed with a mixed solution of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, a sufficient effect can be obtained at a lower concentration than when each is used alone. can get. That is, it has been found that sufficient rust prevention and water wettability can be obtained even if the average thickness of the mixed layer on the surface of the copper foil formed by the surface treatment is thin. Moreover, since ultrasonic weldability will become favorable if the average thickness of a mixed layer is made thin, it can be equipped with the outstanding rust prevention property, water wettability, and ultrasonic weldability with sufficient balance.
アゾール系化合物と分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物とで形成された混合層と銅箔との間には、さらにアゾール系化合物で構成された中間層を形成してもよい。この場合、最表面にはアゾール系化合物と分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物とで形成された混合層が存在するため、上述のように優れた防錆性、水濡れ性及び超音波溶接性をバランス良く備えることができる上、さらに混合層と銅箔との間にアゾール系化合物で構成された中間層が形成されているため、防錆性をより向上させることができる。また、中間層として、クロメート処理層を形成してもよい。クロメート処理層もまた、防錆性を有しているため、クロメート処理層で形成した中間層を設けることによって、防錆性をより向上させることができる。さらに、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物とアゾール系化合物とで形成された混合層と銅箔との間に中間層を設ける代わりに、例えば銅箔表面を分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物で処理しておいて、その上に混合層を設けてもよい。これにより、水濡れ性がさらに向上する。 An intermediate layer composed of an azole compound is further formed between the mixed layer formed of the azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule and the copper foil. Also good. In this case, the outermost surface has a mixed layer formed of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. In addition to providing a good balance between wettability and ultrasonic weldability, an intermediate layer composed of an azole compound is formed between the mixed layer and the copper foil, thus further improving rust prevention. Can do. Further, a chromate treatment layer may be formed as the intermediate layer. Since the chromate treatment layer also has antirust properties, the antirust property can be further improved by providing an intermediate layer formed of the chromate treatment layer. Furthermore, instead of providing an intermediate layer between the copper foil and the mixed layer formed of a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule and an azole compound, the surface of the copper foil is May be treated with a water-soluble organic compound having a hydroxyl group and a linear ether bond, and a mixed layer may be provided thereon. Thereby, water wettability improves further.
アゾール系化合物と分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液により形成された混合層について、その構造を正確に解明することは困難であるが、化学構造解析として、銅箔表面をフーリエ変換型赤外分光装置(FT−IR装置)にて分析することでOH基、Si−OH基、Si−O−Si基を検出し、飛行時間型二次イオン質量分析装置(TOF−SIMS装置)でアゾール系化合物を検出することができる。
以上の検出結果により分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物及びアゾール系化合物の存在を確認した上で、さらにX線光電子分光分析装置(XPS装置)とアルゴンスパッタとを組み合わせて、深さ方向の元素分析を行い、各元素の分布の様子によって、混合層が形成されているのか、又は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物及びアゾール系化合物による単独の層が形成されているのかを判定する。また、当該深さ方向の元素分析により、混合層の厚みを決定する。XPS装置にて、アゾール系化合物と水溶性エポキシ樹脂の加水分解物、二級アミン付加物、又は、イミダゾール化合物付加物の混合層の場合はN及びOを検出し、且つ、C検出量がバックグラウンドレベルよりも大きい深さ範囲を混合層の厚みとしてこれを複数箇所測定し、その平均値D0を混合層の平均厚みとする。また、アゾール系化合物とエポキシ基を付与したシランカップリング剤の加水分解物の混合層ではSi及びNを検出し、且つ、C検出量がバックグラウンドレベルよりも大きい深さ範囲を混合層の厚みとしてこれを複数箇所測定し、その平均値D0を混合層の平均厚みとすることもできる。例として、アゾール系化合物とエポキシ基を加水分解されたシランカップリング剤の混合有機皮膜につき、XPS装置にて分析した結果を図2に示す。なお、密着性、防錆性及び超音波溶接性の共存を図る観点から、混合層の平均厚みD0は1.0〜5.0nmが好ましく、1.5〜4.0nmがより好ましい。また、混合層と銅箔との間にさらに中間層が形成されている場合であっても、混合層及び中間層の合計の平均厚みについて、D0は同様に、1.0〜5.0nmが好ましく、1.5〜4.0nmがより好ましい。また、混合層と中間層とが形成されている場合、それらの厚みの割合として、混合層の方が大きいことが好ましい。図3に、アゾール系化合物及び水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物の有機被膜の厚みを測定する際に得られるXPS装置によるN、O及びCのデプスプロファイルの例を示す。Although it is difficult to elucidate the structure of a mixed layer formed by a mixture of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, chemical structure analysis is difficult. By analyzing the copper foil surface with a Fourier transform infrared spectrometer (FT-IR apparatus), OH groups, Si-OH groups, and Si-O-Si groups are detected, and time-of-flight secondary ion mass spectrometry An azole compound can be detected by a device (TOF-SIMS device).
Based on the above detection results, the presence of water-soluble organic compounds and azole compounds having hydroxyl groups and linear ether bonds in the molecule was confirmed, and an X-ray photoelectron spectrometer (XPS device) and argon sputtering were further combined. Then, elemental analysis in the depth direction is performed, and depending on the distribution of each element, a mixed layer is formed, or a water-soluble organic compound and an azole compound having a hydroxyl group and a linear ether bond in the molecule It is determined whether a single layer is formed. Further, the thickness of the mixed layer is determined by elemental analysis in the depth direction. In the case of a mixed layer of hydrolyzate of azole compound and water-soluble epoxy resin, secondary amine adduct, or imidazole compound adduct in the XPS device, N and O are detected, and the C detection amount is back. This was measured several places a greater depth range than the ground level as the thickness of the mixed layer, the average thickness of the mixture layer and the average value D 0. In the mixed layer of the hydrolyzate of the azole compound and the silane coupling agent having an epoxy group, Si and N are detected, and the depth range in which the C detection amount is larger than the background level is set to the thickness of the mixed layer. It is also possible to measure this at a plurality of locations, and use the average value D 0 as the average thickness of the mixed layer. As an example, FIG. 2 shows the result of analyzing the mixed organic film of an azole compound and a silane coupling agent hydrolyzed with an epoxy group using an XPS apparatus. In addition, from the viewpoint of coexistence of adhesion, rust prevention, and ultrasonic weldability, the average thickness D 0 of the mixed layer is preferably 1.0 to 5.0 nm, and more preferably 1.5 to 4.0 nm. Further, even when an intermediate layer is further formed between the mixed layer and the copper foil, D 0 is similarly 1.0 to 5.0 nm for the total average thickness of the mixed layer and the intermediate layer. Is preferable, and 1.5 to 4.0 nm is more preferable. Moreover, when the mixed layer and the intermediate | middle layer are formed, it is preferable that the mixed layer is larger as a ratio of those thickness. FIG. 3 shows the depth of N, O, and C by an XPS apparatus obtained when measuring the thickness of an organic film of an azole compound and a compound obtained by adding an imidazole group to a water-soluble organic compound having a hydroxyl group and a linear ether bond. An example of a profile is shown.
アゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物は、エタノールや水等の溶媒に溶かして使用することができる。一般に、アゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の濃度を高くすると、形成される有機皮膜が厚くなり、濃度を低くすると薄くなる。両者を混合した溶液で処理することで、アゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の混合層が形成される。 An azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule can be used by dissolving in a solvent such as ethanol or water. Generally, when the concentration of the azole compound and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is increased, the formed organic film is thickened, and the concentration is decreased when the concentration is decreased. By processing with the solution which mixed both, the mixed layer of the water-soluble organic compound which has a hydroxyl group and a linear ether bond in a molecule | numerator is formed.
表面処理で使用するアゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の混合液において、アゾール系化合物の濃度は、0.01〜0.25g/L、好ましくは0.02〜0.2g/Lであり、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の濃度は、0.5〜20g/L、好ましくは1〜10g/Lである。これらの濃度範囲の混合液にて表面処理をすることで、防錆性、水濡れ性及び超音波溶接性のバランスが良好な混合層を形成することができる。 In the mixed solution of the azole compound used in the surface treatment and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, the concentration of the azole compound is 0.01 to 0.25 g / L, preferably 0. The concentration of the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is 0.5 to 20 g / L, preferably 1 to 10 g / L. By performing a surface treatment with a mixed solution in these concentration ranges, a mixed layer having a good balance of rust prevention, water wettability and ultrasonic weldability can be formed.
本発明に係る銅箔を材料とする集電体とその上に形成された活物質層によって構成された負極を用いて、慣用手段によりリチウムイオン電池を作製することができる。リチウムイオン電池には、電解質中のリチウムイオンが電気伝導を担うリチウムイオン一次電池用及びリチウムイオン二次電池が含まれる。負極活物質としては、限定的ではないが、炭素、珪素、スズ、ゲルマニウム、鉛、アンチモン、アルミニウム、インジウム、リチウム、酸化スズ、チタン酸リチウム、窒化リチウム、インジウムを固溶した酸化錫、インジウム−錫合金、リチウム−アルミニウム合金、リチウム−インジウム合金等が挙げられる。 A lithium ion battery can be produced by conventional means using a negative electrode composed of a current collector made of the copper foil according to the present invention and an active material layer formed thereon. The lithium ion battery includes a lithium ion primary battery and a lithium ion secondary battery in which lithium ions in the electrolyte are responsible for electrical conduction. Examples of the negative electrode active material include, but are not limited to, carbon, silicon, tin, germanium, lead, antimony, aluminum, indium, lithium, tin oxide, lithium titanate, lithium nitride, indium-tin oxide, indium- Examples thereof include a tin alloy, a lithium-aluminum alloy, and a lithium-indium alloy.
以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。
(実施例1)
アゾール系化合物及び水溶性エポキシ樹脂の混合液による表面処理が特性に与える影響を検討するため、以下の条件で実施例及び比較例を作成した。各種条件及び試験結果を後述の表1に示す。
[圧延銅箔の製造]
厚さ200mm、幅600mmのタフピッチ銅のインゴットを製造し、熱間圧延により10mmまで圧延した。
次に、焼鈍と冷間圧延を繰り返し、最後に冷間圧延で、ワークロール径60mm、ワークロール表面粗さRaを0.03μmとし、最終パスの圧延速度400m/分、加工度20%として厚さ10μmに仕上げた。圧延油の粘度は9.0cSt(25℃)であった。得られた圧延銅箔はRaが0.11μmであった。EXAMPLES Examples of the present invention will be described below, but these are provided for better understanding of the present invention and are not intended to limit the present invention.
Example 1
In order to examine the effect of surface treatment with a mixed solution of an azole compound and a water-soluble epoxy resin on properties, Examples and Comparative Examples were created under the following conditions. Various conditions and test results are shown in Table 1 below.
[Manufacture of rolled copper foil]
A tough pitch copper ingot having a thickness of 200 mm and a width of 600 mm was manufactured and rolled to 10 mm by hot rolling.
Next, annealing and cold rolling are repeated, and finally, by cold rolling, the work roll diameter is 60 mm, the work roll surface roughness Ra is 0.03 μm, the final pass rolling speed is 400 m / min, and the workability is 20%. It finished to 10 μm. The viscosity of the rolling oil was 9.0 cSt (25 ° C.). The obtained rolled copper foil had an Ra of 0.11 μm.
[電解銅箔の製造]
特許第4115240号の実施例に記載された電解液を用いて電解して、10μmの電解銅箔を製造した。得られた電解銅箔はRaが0.12μmであった。[Manufacture of electrolytic copper foil]
It electrolyzed using the electrolyte solution described in the Example of
[表面処理]
上記の通り製造した板厚10μmの圧延銅箔及び電解銅箔につき、表1に記載の濃度のアゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物各単独の水溶液、及び、両者を混合した水溶液を準備し、これに3秒間浸漬した後、ドライヤーにて乾燥した。アゾール系化合物は、1,2,3−ベンゾトリアゾール(以下、BTA)を、また、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物は、下記反応式(6)に示すとおり、ナガセケムテックス社製の「デナコールEX−521」のエポキシ基を開環させて水酸基を付加したものを用いた。
About the rolled copper foil and the electrolytic copper foil having a thickness of 10 μm produced as described above, the azole-based compound having the concentration shown in Table 1 and the aqueous solution of each water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, And the aqueous solution which mixed both was prepared, after being immersed in this for 3 second, it dried with the dryer. The azole compound is 1,2,3-benzotriazole (hereinafter referred to as BTA), and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is represented by the following reaction formula (6): A product obtained by opening the epoxy group of “Denacol EX-521” manufactured by Nagase ChemteX Corporation and adding a hydroxyl group was used.
[防錆性]
(1)銅箔を30mm×60mmの大きさに切り出した。
(2)試料(1)を硫化水素暴露試験機(H2S:3ppm、40℃、50RH%)に入れ、20分間保持した。
(3)試料を(2)の試験機から取り出し、銅箔表面の色調を確認した。
(4)試験後の銅箔表面の色調が試験前と同じものを「○」、試験前と比較して、薄い赤褐色に変色したものを「△」、表面全体が紫あるいは青色に変色したものを「×」とした。[Rust prevention]
(1) A copper foil was cut into a size of 30 mm × 60 mm.
(2) Sample (1) was placed in a hydrogen sulfide exposure tester (H2S: 3 ppm, 40 ° C., 50 RH%) and held for 20 minutes.
(3) The sample was taken out from the testing machine of (2), and the color tone of the copper foil surface was confirmed.
(4) “○” indicates the same color tone of the copper foil surface after the test as before the test, “△” indicates that the color changed to light reddish brown compared to before the test, and the entire surface changes to purple or blue Was marked “x”.
[水濡れ性]
協和界面科学株式会社製接触角計CA−D型を用い、室温(25℃)にて1.52mmφの純水の液滴を滴下することで接触角を測定し、接触角60°未満を「◎」、60〜70°を「○」、70〜80°を「△」、80°を超えると「×」とした。[Water wettability]
Using a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd., a contact angle was measured by dropping a drop of 1.52 mmφ pure water at room temperature (25 ° C.). “◎”, 60-70 ° is “◯”, 70-80 ° is “Δ”, and 80 ° is “X”.
[超音波溶接性]
(1)銅箔を100mm×150mmの大きさに切り出し、30枚重ねた。
(2)ブランソン社製のアクチュエータ(型番:Ultraweld L20E)にホーン(ピッチ0.8mm、高さ0.4mm)を取り付けた。アンビルは0.2mmピッチを使用した。
(3)溶接条件は、圧力40psi、振幅60μm、振動数20kHz、溶接時間は0.1秒とした。
(4)上記条件で溶接した後、銅箔を1枚ずつ剥離したときに、21枚以上の銅箔が溶接部分で破れた場合を「◎」、11〜20枚の銅箔が溶接部分で破れた場合を「○」、1〜10枚の銅箔が溶接部分で破れた場合を「△」、一枚も銅箔が破れなかった場合を「×」とした。なお、銅箔を剥離する前に、ホーンに接触していた最表層の銅箔の溶接部分を実態顕微鏡にて20倍で拡大観察し、クラックが発生していないことを確認してから剥離試験を実施した。[Ultrasonic weldability]
(1) The copper foil was cut into a size of 100 mm × 150 mm, and 30 sheets were stacked.
(2) A horn (pitch 0.8 mm, height 0.4 mm) was attached to an actuator (model number: Ultraweld L20E) manufactured by Branson. The anvil used a 0.2 mm pitch.
(3) The welding conditions were a pressure of 40 psi, an amplitude of 60 μm, a vibration frequency of 20 kHz, and a welding time of 0.1 second.
(4) After welding under the above conditions, when the copper foil is peeled one by one, the case where 21 or more copper foils are torn at the welded part is “◎”, and 11 to 20 copper foils are the welded part. The case where it was torn was designated as “◯”, the case where 1 to 10 copper foils were torn at the welded portion, “Δ”, and the case where no copper foil was torn was designated as “x”. Before peeling the copper foil, the welded portion of the outermost copper foil that was in contact with the horn was magnified 20 times with an actual microscope to confirm that there were no cracks before peeling test Carried out.
[有機皮膜の厚み]
有機皮膜(混合層、又は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物又はBTA単独で形成された層)の厚みは、アルゴンスパッタしながらXPS装置で銅箔の深さ方向について元素分析し、O及びNを検出し、且つ、C検出量がバックグラウンドレベルよりも大きな深さ範囲(SiO2換算)を有機皮膜厚みとし、任意の5カ所の平均値を有機皮膜厚みの平均値とした。
・装置:XPS装置(アルバックファイ社、型式5600MC)
・真空度:5.7×10-7Pa
・X線:単色AlKα、X線出力210W、入射角45°、取り出し角45°
・イオン線:イオン種Ar+、加速電圧3kV、掃引面積3mm×3mm、スパッタリングレート2.3nm/min(SiO2換算)[Thickness of organic film]
The thickness of the organic film (mixed layer or a layer formed of a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule or BTA alone) is measured in the depth direction of the copper foil with an XPS apparatus while sputtering with argon. The elemental analysis was performed, O and N were detected, and the depth of the C detected amount larger than the background level (in terms of SiO 2 ) was defined as the organic film thickness, and the average value of any five locations was the organic film thickness. The average value was used.
-Equipment: XPS equipment (ULVAC-PHI, Model 5600MC)
・ Degree of vacuum: 5.7 × 10 −7 Pa
X-ray: Monochromatic AlKα, X-ray output 210W, incident angle 45 °, extraction angle 45 °
Ion beam: ion species Ar + ,
(評価結果)
実施例1−1〜1−11は、BTAと分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液で表面処理をしており、更に、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合有機皮膜厚が1.0〜5.0nmの範囲にある。このため、水濡れ性、防錆性及び溶接性の全てにおいて良好な特性を示している。
比較例1−12は、表面処理未実施であり、表面に有機皮膜が存在せず、溶接性は良好で水濡れ性も悪くはないが、防錆性が悪く、水濡れ性、防錆性及び溶接性を同時に満足させることはできない。
比較例1−13〜1−15は、BTAのみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど防錆性が良好である。しかしながら、いずれの濃度であっても水濡れ性が悪く、BTAのみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
比較例1−16〜1−18は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物のみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど水濡れ性が良好である。しかしながら、いずれの濃度であっても防錆性が悪く、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物のみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
また、比較例1−19は、BTAのみで表面処理を行った後、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物で表面処理を行っており、BTAの防錆効果が低下している。
また、比較例1−20は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物のみで表面処理を行った後、BTAで表面処理を行っており、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の水濡れ性改善効果が低下している。(Evaluation results)
Examples 1-1 to 1-11 are surface-treated with a mixed solution of BTA and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and further, hydroxyl group and linear in the molecule. The mixed organic film thickness with a water-soluble organic compound having an ether bond is in the range of 1.0 to 5.0 nm. For this reason, it has shown favorable characteristics in all of water wettability, rust prevention property, and weldability.
In Comparative Example 1-12, the surface treatment was not performed, the organic film was not present on the surface, the weldability was good and the water wettability was not bad, but the rust preventive property was poor, the water wettability and the rust preventive property. And weldability cannot be satisfied at the same time.
In Comparative Examples 1-13 to 1-15, the surface treatment is performed only with BTA, and the weldability is better as the treatment liquid concentration is lower, and the rust prevention is better as the treatment liquid concentration is higher. However, the water wettability is poor at any concentration, and only BTA indicates that water wettability, rust prevention and weldability cannot be satisfied at the same time.
Comparative Examples 1-16 to 1-18 are surface-treated only with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and the lower the treatment liquid concentration, the better the weldability. The higher the concentration, the better the water wettability. However, the rust prevention property is poor at any concentration, and only a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule can simultaneously satisfy water wettability, rust prevention property and weldability. Indicates that it is not possible.
In Comparative Example 1-19, the surface treatment was performed only with BTA, and then the surface treatment was performed with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. doing.
In Comparative Example 1-20, the surface treatment was performed only with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and then the surface treatment was performed with BTA. The water wettability improving effect of the water-soluble organic compound having an ether bond is reduced.
(実施例2)
以下の方法で表面処理した試料につき、実施例1に従い評価した。各種条件及び試験結果を後述の表2に示す。
[表面処理]
実施例1の通り製造した板厚10μmの圧延銅箔及び電解銅箔につき、表1に記載の濃度のアゾール系化合物及びエポキシ基を加水分解させたシランカップリング剤各単独の水溶液、及び、両者を混合した水溶液を準備し、これに3秒間浸漬した後、ドライヤーにて乾燥した。アゾール系化合物は、1,2,3−ベンゾトリアゾール(以下、BTA)また、エポキシ基を加水分解させたシランカップリング剤として、下記一般式(H)の化合物を用いた。
The sample surface-treated by the following method was evaluated according to Example 1. Various conditions and test results are shown in Table 2 below.
[surface treatment]
About the rolled copper foil and the electrolytic copper foil having a thickness of 10 μm manufactured as in Example 1, the azole-based compound having the concentration shown in Table 1 and the aqueous solution of each silane coupling agent obtained by hydrolyzing the epoxy group, and both A mixed aqueous solution was prepared, dipped in this for 3 seconds, and then dried with a dryer. As the azole compound, 1,2,3-benzotriazole (hereinafter referred to as BTA), and a compound represented by the following general formula (H) was used as a silane coupling agent obtained by hydrolyzing an epoxy group.
(評価結果)
実施例2−1〜2−11は、BTAとエポキシ基を加水分解させたシランカップリング剤との混合液で表面処理をしており、更に、エポキシ基を加水分解させたシランカップリング剤との混合有機皮膜厚が1.0〜5.0nmの範囲にある。このため、水濡れ性、防錆性及び溶接性の全てにおいて良好な特性を示している。
比較例2−12は、表面処理未実施であり、表面に有機皮膜が存在せず、溶接性は良好で水濡れ性も悪くはないが、防錆性が悪く、水濡れ性、防錆性及び溶接性を同時に満足させることはできない。
比較例2−13〜2−15は、BTAのみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど防錆性が良好である。しかしながら、いずれの濃度であっても水濡れ性が悪く、BTAのみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
比較例2−16〜2−18は、エポキシ基を加水分解させたシランカップリング剤のみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど水濡れ性が良好である。しかしながら、いずれの濃度であっても防錆性が悪く、エポキシ基を加水分解させたシランカップリング剤のみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
また、比較例2−19は、BTAのみで表面処理を行った後、エポキシ基を加水分解させたシランカップリング剤で表面処理を行っており、BTAの防錆効果が低下している。
また、比較例2−20は、エポキシ基を加水分解させたシランカップリング剤のみで表面処理を行った後、BTAで表面処理を行っており、エポキシ基を加水分解させたシランカップリング剤の水濡れ性改善効果が低下している。(Evaluation results)
Examples 2-1 to 2-11 are surface-treated with a mixed solution of BTA and a silane coupling agent obtained by hydrolyzing an epoxy group, and further, a silane coupling agent obtained by hydrolyzing an epoxy group and The mixed organic film thickness is in the range of 1.0 to 5.0 nm. For this reason, it has shown favorable characteristics in all of water wettability, rust prevention property, and weldability.
In Comparative Example 2-12, the surface treatment was not performed, the organic film was not present on the surface, the weldability was good and the water wettability was not bad, but the rust preventive property was poor, the water wettability and the rust preventive property. And weldability cannot be satisfied at the same time.
Comparative Examples 2-13 to 2-15 are surface-treated only with BTA. The lower the treatment liquid concentration, the better the weldability, and the higher the treatment liquid concentration, the better the rust prevention property. However, the water wettability is poor at any concentration, and only BTA indicates that water wettability, rust prevention and weldability cannot be satisfied at the same time.
In Comparative Examples 2-16 to 2-18, the surface treatment was performed only with the silane coupling agent obtained by hydrolyzing the epoxy group. The lower the treatment liquid concentration, the better the weldability, and the higher the treatment liquid concentration, the more water. Good wettability. However, it shows that the rust prevention property is poor at any concentration, and it is not possible to satisfy water wettability, rust prevention property and weldability at the same time with only the silane coupling agent hydrolyzed epoxy group. Yes.
In Comparative Example 2-19, the surface treatment was performed only with BTA, and then the surface treatment was performed with a silane coupling agent obtained by hydrolyzing an epoxy group, and the rust prevention effect of BTA was lowered.
In Comparative Example 2-20, the surface treatment was performed only with the silane coupling agent obtained by hydrolyzing the epoxy group, and then the surface treatment was performed with BTA, and the silane coupling agent obtained by hydrolyzing the epoxy group. The effect of improving water wettability is reduced.
(実施例3)
以下の方法で表面処理した試料につき、実施例1に従い評価した。各種条件及び試験結果を後述の表3に示す。
[表面処理]
実施例1の通り製造した板厚10μmの圧延銅箔及び電解銅箔につき、表3に記載の濃度のアゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物各単独の水溶液、及び、両者を混合した水溶液を準備し、これに3秒間浸漬した後、ドライヤーにて乾燥した。アゾール系化合物は、1,2,3−ベンゾトリアゾール(以下、BTA)また、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物は、下記反応式(7)に示すとおり、ナガセケムテックス社製の「デナコールEX−521」のエポキシ基にイミダゾールを付加反応させたものを用いた。
The sample surface-treated by the following method was evaluated according to Example 1. Various conditions and test results are shown in Table 3 below.
[surface treatment]
About the rolled copper foil and the electrolytic copper foil having a thickness of 10 μm manufactured as in Example 1, the azole group compound having the concentration shown in Table 3 and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule are imidazole groups. An aqueous solution of each of the compounds to which was added and an aqueous solution in which both were mixed were prepared, immersed in this for 3 seconds, and then dried with a drier. The azole compound is 1,2,3-benzotriazole (hereinafter referred to as BTA), and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is Nagase Chem as shown in the following reaction formula (7). A product obtained by adding imidazole to an epoxy group of “Denacol EX-521” manufactured by Tex Co., Ltd. was used.
(評価結果)
実施例3−1〜3−11は、BTAと分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物との混合液で表面処理をしており、更に、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物との混合有機皮膜厚が1.0〜5.0nmの範囲にある。このため、水濡れ性、防錆性及び溶接性の全てにおいて良好な特性を示している。
比較例3−12は、表面処理未実施であり、表面に有機皮膜が存在せず、溶接性は良好で水濡れ性も悪くはないが、防錆性が悪く、水濡れ性、防錆性及び溶接性を同時に満足させることはできない。
比較例3−13〜3−15は、BTAのみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど防錆性が良好である。しかしながら、いずれの濃度であっても水濡れ性が悪く、BTAのみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
比較例3−16〜3−18は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物のみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど水濡れ性が良好である。しかしながら、いずれの濃度であっても防錆性が悪く、分子中に水酸基と線状エーテル結合を有する水溶性有機化合物にイミダゾール基を付加した化合物のみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
また、比較例3−19は、BTAのみで表面処理を行った後、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物で表面処理を行っており、BTAの防錆効果が低下している。
また、比較例3−20は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物のみで表面処理を行った後、BTAで表面処理を行っており、分子中に水酸基と線状エーテル結合を有する水溶性有機化合物にイミダゾール基を付加した化合物の水濡れ性改善効果が低下している。(Evaluation results)
Examples 3-1 to 3-11 are surface-treated with a mixture of BTA and a compound obtained by adding an imidazole group to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. The mixed organic film thickness with the compound which added the imidazole group to the water-soluble organic compound which has a hydroxyl group and a linear ether bond in a molecule | numerator exists in the range of 1.0-5.0 nm. For this reason, it has shown favorable characteristics in all of water wettability, rust prevention property, and weldability.
In Comparative Example 3-12, the surface treatment was not performed, the organic film was not present on the surface, the weldability was good and the water wettability was not bad, but the rust preventive property was poor, the water wettability and the rust preventive property. And weldability cannot be satisfied at the same time.
Comparative Examples 3-13 to 3-15 are surface-treated only with BTA. The lower the treatment liquid concentration, the better the weldability, and the higher the treatment liquid concentration, the better the rust prevention property. However, the water wettability is poor at any concentration, and only BTA indicates that water wettability, rust prevention and weldability cannot be satisfied at the same time.
In Comparative Examples 3-16 to 3-18, surface treatment is performed only with a compound in which an imidazole group is added to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and welding is performed as the concentration of the treatment liquid decreases. The wettability is better as the treatment solution concentration is higher. However, the rust prevention property is poor at any concentration, and with only a compound having an imidazole group added to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, water wettability, rust prevention property and weldability It cannot be satisfied at the same time.
In Comparative Example 3-19, after surface treatment with only BTA, surface treatment was performed with a compound in which an imidazole group was added to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. The antirust effect of BTA is reduced.
In Comparative Example 3-20, surface treatment was performed only with a compound in which an imidazole group was added to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and then surface treatment was performed with BTA. The effect of improving the wettability of a compound obtained by adding an imidazole group to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is low.
(実施例4)
以下の方法で表面処理した試料につき、実施例1で記載の方法又は以下の方法で評価した。各種条件及び試験結果を後述の表4に示す。Example 4
The sample surface-treated by the following method was evaluated by the method described in Example 1 or the following method. Various conditions and test results are shown in Table 4 below.
[圧延銅箔の製造]
無酸素銅に各種元素を添加し、厚さ200mm、幅600mmの銅合金インゴットを製造し、熱間圧延により10mmまで圧延した。
次に、焼鈍と冷間圧延を繰り返し、最後に冷間圧延で、ワークロール径60mm、ワークロール表面粗さRaを0.03μmとし、最終パスの圧延速度400m/分、加工度20%として厚さ6〜20μmに仕上げた。圧延油の粘度は9.0cSt(25℃)であった。得られた圧延銅箔はRaが0.11μmであった。[Manufacture of rolled copper foil]
Various elements were added to oxygen-free copper to produce a copper alloy ingot having a thickness of 200 mm and a width of 600 mm, and rolled to 10 mm by hot rolling.
Next, annealing and cold rolling are repeated, and finally, by cold rolling, the work roll diameter is 60 mm, the work roll surface roughness Ra is 0.03 μm, the final pass rolling speed is 400 m / min, and the workability is 20%. It finished to 6-20 μm. The viscosity of the rolling oil was 9.0 cSt (25 ° C.). The obtained rolled copper foil had an Ra of 0.11 μm.
[表面処理]
上記の通り製造した板厚6〜20μmの圧延銅箔につき、表4に記載の濃度のアゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物各単独の水溶液、及び、両者を混合した水溶液を準備し、これに5秒間浸漬した後、ドライヤーにて乾燥した。アゾール系化合物は、1,2,3−ベンゾトリアゾール(以下、BTA)を、また、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物は、ナガセケムテックス社製の「デナコールEX−521」のエポキシ基を開環させて水酸基を付加したものを用いた。[surface treatment]
About the rolled copper foil having a plate thickness of 6 to 20 μm produced as described above, an azole compound having a concentration shown in Table 4 and an aqueous solution of each water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and An aqueous solution in which both were mixed was prepared, immersed in this for 5 seconds, and then dried with a dryer. The azole compound is 1,2,3-benzotriazole (hereinafter referred to as BTA), and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is "Denacol EX-" manufactured by Nagase ChemteX Corporation. 521 "was used by opening the epoxy group and adding a hydroxyl group.
[超音波溶接性]
(1)銅箔を100mm×150mmの大きさに切り出し、板厚6μmでは50枚、板厚10μmでは30枚、板厚20μmでは15枚重ねた。
(2)ブランソン社製のアクチュエータ(型番:Ultraweld L20E)にホーン(ピッチ0.8mm、高さ0.4mm)を取り付けた。アンビルは0.2mmピッチを使用した。
(3)溶接条件は、圧力40psi、振幅60μm、振動数20kHz、溶接時間は0.1秒とした。
(4)上記条件で溶接した後、銅箔を1枚ずつ剥離したときに、板厚6μmでは35枚以上、板厚10μmでは21枚以上、板厚20μmでは11枚以上の銅箔が溶接部分で破れた場合を「◎」、板厚6μmでは18〜34枚、板厚10μmでは11〜20枚、板厚20μmでは6〜10枚の銅箔が溶接部分で破れた場合を「○」、板厚6μmでは1〜17枚、板厚10μmでは1〜10枚、板厚20μmでは1〜5枚の銅箔が溶接部分で破れた場合を「△」、一枚も銅箔が破れなかった場合を「×」とした。なお、銅箔を剥離する前に、ホーンに接触していた最表層の銅箔の溶接部分を実態顕微鏡にて20倍で拡大観察し、クラックが発生していないことを確認してから剥離試験を実施した。[Ultrasonic weldability]
(1) Copper foil was cut into a size of 100 mm × 150 mm, and 50 sheets were stacked at a plate thickness of 6 μm, 30 sheets were stacked at a plate thickness of 10 μm, and 15 plates were stacked at a plate thickness of 20 μm.
(2) A horn (pitch 0.8 mm, height 0.4 mm) was attached to an actuator (model number: Ultraweld L20E) manufactured by Branson. The anvil used a 0.2 mm pitch.
(3) The welding conditions were a pressure of 40 psi, an amplitude of 60 μm, a vibration frequency of 20 kHz, and a welding time of 0.1 second.
(4) When the copper foils are peeled one by one after welding under the above conditions, 35 or more copper foils with a plate thickness of 6 μm, 21 or more copper plates with a plate thickness of 10 μm, and 11 or more copper foils with a plate thickness of 20 μm "◎" when the plate is torn, 18 to 34 when the plate thickness is 6 µm, 11 to 20 when the plate thickness is 10 µm, and 6 to 10 when the plate thickness is 20 µm, "○" When the plate thickness is 6 μm, 1 to 17 sheets, when the plate thickness is 10 μm, 1 to 10 sheets, and when the plate thickness is 20 μm, 1 to 5 copper foils were torn at the welded portion, “△”, and no copper foil was torn. The case was set as “x”. Before peeling the copper foil, the welded portion of the outermost copper foil that was in contact with the horn was magnified 20 times with an actual microscope to confirm that there were no cracks before peeling test Carried out.
[その他の評価]
水濡れ性、防錆性及び有機皮膜の厚みは、実施例1に記載の方法で評価した。[Other evaluations]
Water wettability, rust prevention, and the thickness of the organic film were evaluated by the method described in Example 1.
(評価結果)
実施例4−1〜4−9は、BTAと分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液で表面処理をしており、更に、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合有機皮膜厚が1.0〜5.0nmの範囲にある。このため、各種銅合金においても、水濡れ性、防錆性及び溶接性の全てにおいて良好な特性を示している。比較例4−10は、BTAのみで表面処理を行った後、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物で表面処理を行っており、BTAの防錆効果が低下している。比較例4−11は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物のみで表面処理を行った後、BTAで表面処理を行っており、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の水濡れ性改善効果が低下している。(Evaluation results)
Examples 4-1 to 4-9 are surface-treated with a mixed solution of BTA and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and further, a hydroxyl group and a linear molecule in the molecule. The mixed organic film thickness with a water-soluble organic compound having an ether bond is in the range of 1.0 to 5.0 nm. For this reason, various copper alloys also show good characteristics in all of wettability, rust prevention and weldability. In Comparative Example 4-10, after surface treatment with only BTA, surface treatment is performed with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and the rust prevention effect of BTA is reduced. Yes. In Comparative Example 4-11, the surface treatment was performed only with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and then the surface treatment was performed with BTA. The hydroxyl group and the linear ether bond were contained in the molecule. The effect of improving water wettability of a water-soluble organic compound having
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