WO2016060037A1 - アルミニウム板およびアルミニウム板の製造方法 - Google Patents
アルミニウム板およびアルミニウム板の製造方法 Download PDFInfo
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- WO2016060037A1 WO2016060037A1 PCT/JP2015/078458 JP2015078458W WO2016060037A1 WO 2016060037 A1 WO2016060037 A1 WO 2016060037A1 JP 2015078458 W JP2015078458 W JP 2015078458W WO 2016060037 A1 WO2016060037 A1 WO 2016060037A1
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- WO
- WIPO (PCT)
- Prior art keywords
- aluminum plate
- hole
- aluminum
- film
- acid
- Prior art date
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 234
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 229
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 claims description 66
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 61
- 238000004090 dissolution Methods 0.000 claims description 52
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 51
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 33
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 31
- 229910017604 nitric acid Inorganic materials 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 230000000149 penetrating effect Effects 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 239000011149 active material Substances 0.000 abstract description 66
- 239000002585 base Substances 0.000 description 34
- 239000010410 layer Substances 0.000 description 33
- 229910052751 metal Inorganic materials 0.000 description 30
- 239000002184 metal Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 24
- 239000008151 electrolyte solution Substances 0.000 description 21
- 238000005868 electrolysis reaction Methods 0.000 description 20
- 238000007747 plating Methods 0.000 description 17
- 230000005611 electricity Effects 0.000 description 16
- -1 nitrate compound Chemical class 0.000 description 15
- 238000007788 roughening Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005530 etching Methods 0.000 description 12
- 239000003513 alkali Substances 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 150000001553 barium compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- SIWNEELMSUHJGO-UHFFFAOYSA-N 2-(4-bromophenyl)-4,5,6,7-tetrahydro-[1,3]oxazolo[4,5-c]pyridine Chemical compound C1=CC(Br)=CC=C1C(O1)=NC2=C1CCNC2 SIWNEELMSUHJGO-UHFFFAOYSA-N 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 1
- 229940094800 barium oxalate Drugs 0.000 description 1
- OOULUYZFLXDWDQ-UHFFFAOYSA-L barium perchlorate Chemical compound [Ba+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O OOULUYZFLXDWDQ-UHFFFAOYSA-L 0.000 description 1
- ARSLNKYOPNUFFY-UHFFFAOYSA-L barium sulfite Chemical compound [Ba+2].[O-]S([O-])=O ARSLNKYOPNUFFY-UHFFFAOYSA-L 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- HLKMEIITONDPGG-UHFFFAOYSA-L barium(2+);2-hydroxypropanoate Chemical compound [Ba+2].CC(O)C([O-])=O.CC(O)C([O-])=O HLKMEIITONDPGG-UHFFFAOYSA-L 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940111685 dibasic potassium phosphate Drugs 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZGJOORCILCWISV-UHFFFAOYSA-L magnesium difluoride pentahydrate Chemical compound O.O.O.O.O.[F-].[F-].[Mg++] ZGJOORCILCWISV-UHFFFAOYSA-L 0.000 description 1
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
- 235000013926 potassium gluconate Nutrition 0.000 description 1
- 229960003189 potassium gluconate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ZLIBICFPKPWGIZ-UHFFFAOYSA-N pyrimethanil Chemical compound CC1=CC(C)=NC(NC=2C=CC=CC=2)=N1 ZLIBICFPKPWGIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/04—Etching of light metals
-
- 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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/12—Electrolytic coating other than with metals with inorganic materials by cathodic processes on light metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/14—Etching locally
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
- H01M4/661—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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- 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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/742—Meshes or woven material; Expanded metal perforated material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to an aluminum plate used for a current collector for an electricity storage device and the like, and a method for producing the aluminum plate.
- an aluminum plate is used as an electrode current collector (hereinafter simply referred to as “current collector”) used for the positive electrode or the negative electrode of such an electricity storage device. It is also known that an active material such as activated carbon is applied to the surface of a current collector made of an aluminum plate and used as a positive electrode or a negative electrode.
- Patent Document 1 describes that an aluminum through foil is used as a current collector, and describes that an active material is applied to the aluminum through foil ([Claim 1] [ 0036]).
- Patent Document 2 describes a perforated current collector made of a metal foil in which a large number of through holes are provided by etching, and describes that an active material is applied to the current collector. ([Claim 1] [0002]).
- the through-hole is formed to facilitate the movement of lithium ions.
- the lithium ions When lithium ions are pre-doped, the lithium ions permeate through the through-holes and diffuse to the negative electrode. Doped. Therefore, it is desirable that a large number of through holes be formed in order to efficiently perform pre-doping.
- the through hole formed by punching or the like is a large hole having a diameter of 300 ⁇ m or more.
- the current collector is a thin plate-like member, if the diameter of the through hole is large, the strength of the current collector is lowered.
- the surface of the applied active material may have irregularities corresponding to the through-holes of the current collector, or may pass through the surface, thereby impairing the uniformity of the active material surface. The nature will decline.
- Patent Document 1 describes that the inside diameter of a through-hole is set in a range of 0.2 to 5 ⁇ m to prevent the applied active material from falling through ([0032] [0036]). .
- Patent Document 2 when various active materials are applied to an aluminum plate, there is a problem that the adhesiveness between the aluminum plate and the active material is weak and the active material is easily dropped. ([0003]). When the active material is dropped after the secondary battery is manufactured, there arises a problem that the charge / discharge capacity is lowered.
- the shape of the through hole is such that the intercept angle ⁇ 1 formed by the back surface of the metal foil and the inner wall surface of the through hole on the back surface side of the metal foil is 10 ° to 80 °.
- the active material to be applied is locked to the through hole by setting the intercept angle ⁇ 2 formed between the surface of the metal foil and the inner wall surface of the through hole on the surface side of the metal foil to 90 ° to 170 °. It is described that the active material is prevented from falling off ([0005]).
- a perforated resist film having a large number of through holes is joined to the surface of a non-porous metal foil.
- a method of etching a three-layer laminate formed by bonding a non-porous resist film to the back surface of a metal foil is disclosed ([0016]).
- the opening diameter of the through hole described in Patent Document 2 is 0.1 mm to 3 mm, and the method described in Patent Document 2 forms a through hole having a finer diameter and an inclined inner wall surface. It was difficult to do.
- an object of the present invention is to provide an aluminum plate having good coatability and high adhesion to an active material and a method for producing the aluminum plate.
- the present inventor has an average opening diameter of the through holes of 0.1 ⁇ m or more and less than 100 ⁇ m, and is a shape having the maximum diameter Ra inside, and the maximum diameter Ra and the minimum diameter Rb. And having a through-hole A having a shape satisfying 1> Rb / Ra ⁇ 0.1, it was found that applicability could be improved and adhesion with the active material could be improved, and the present invention was completed. . That is, it has been found that the above object can be achieved by the following configuration.
- the manufacturing method of the aluminum plate which has a film removal process of removing an aluminum hydroxide film after a through-hole formation process.
- the film forming step includes forming an aluminum hydroxide film by performing electrochemical treatment using nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, or a mixed acid of two or more thereof. Manufacturing method of aluminum plate.
- the through-hole forming step performs electrochemical dissolution treatment using nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, or a mixed acid of two or more thereof to form a through-hole [11] or [ 12]
- the manufacturing method of the aluminum plate of description [14]
- the film removal step removes the aluminum hydroxide film by performing a chemical dissolution treatment using nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, a mixed acid of two or more of these, or sodium hydroxide.
- the method for producing an aluminum plate according to any one of [11] to [13].
- an aluminum plate having good coatability and high adhesion to an active material it is possible to provide an aluminum plate having good coatability and high adhesion to an active material, and a method for producing the aluminum plate.
- FIG. 1A is a top view conceptually showing an example of the aluminum plate of the present invention
- FIG. 1B is a cross-sectional view taken along the line BB of FIG. 1A.
- 2 is an enlarged cross-sectional view of the through hole of the aluminum plate shown in FIG.
- FIG. 3 is a schematic cross-sectional view showing another example of the aluminum plate of the present invention.
- 4 (A) to 4 (E) are schematic cross-sectional views for explaining an example of a preferred method for producing the aluminum plate of the present invention
- FIG. 4 (A) is a schematic view of an aluminum substrate.
- FIG. 4 (B) is a schematic cross-sectional view showing a state in which an oxide film is formed on the surface of the aluminum substrate
- FIG. 4 (C) is an oxide film formation
- FIG. 4D is a schematic cross-sectional view showing a state in which an electrochemical dissolution treatment is performed after the treatment and through holes are formed in the aluminum base material and the oxide film
- FIG. 4D shows the oxide film after the electrochemical dissolution treatment
- FIG. 4E is a schematic cross-sectional view showing the state after the electrochemical roughening treatment is performed after removing the oxide film. is there.
- 5 (A) to 5 (E) are schematic cross-sectional views for explaining another example of the preferred method for producing the aluminum plate of the present invention, and FIG. 5 (A) shows an aluminum substrate.
- FIG. 5 (A) shows an aluminum substrate.
- FIG. 5 (B) is a schematic cross-sectional view showing a state in which an oxide film is formed on the aluminum base and an oxide film is formed on the front and back surfaces.
- FIG. 5D is a schematic cross-sectional view showing a state in which an electrochemical dissolution process is performed after the oxide film formation process and through holes are formed in the aluminum base material and the oxide film.
- FIG. 5D is a diagram of the electrochemical dissolution process.
- FIG. 5E is a schematic cross-sectional view showing a state after the oxide film is removed later, and FIG. 5E is a schematic view showing a state after the electrochemical film is further removed after the oxide film is removed.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the aluminum plate of the present invention is an aluminum plate having a plurality of through holes penetrating in the thickness direction, and the average opening diameter of the through holes is 0.1 ⁇ m or more and less than 100 ⁇ m, and the inside has a maximum diameter Ra.
- the aluminum plate has a through hole A having a shape in which the maximum diameter Ra and the minimum diameter Rb satisfy 1> Rb / Ra ⁇ 0.1.
- FIG. 1 (A) is a schematic top view showing an example of a preferred embodiment of the aluminum plate of the present invention
- FIG. 1 (B) is a cross-sectional view taken along the line BB of FIG. 1 (A).
- FIG. 1C is a schematic cross-sectional view showing an example of an electrode using the aluminum plate 10 shown in FIG. 1A as a current collector of an electricity storage device.
- the aluminum plate 10 is formed by forming a plurality of through holes 5 penetrating in the thickness direction in the aluminum base 3.
- the electrode 30 shown in FIG. 1C is formed by laminating an active material layer 32 on both main surfaces of the aluminum plate 10 shown in FIG. 1B. As shown in the figure, the active material layer 32 is also filled in the through hole 5 and integrated with the active material layer 32 formed on both surfaces.
- the plurality of through-holes 5 formed in the aluminum base 3 have an average opening diameter of 0.1 ⁇ m or more and less than 100 ⁇ m, and a shape having a maximum diameter Ra inside, and the maximum diameter Ra and the minimum diameter Rb are 1> A through hole A having a shape satisfying Rb / Ra ⁇ 0.1 is provided.
- FIG. 2 is an enlarged cross-sectional view of the through hole 5 of the aluminum plate 10 shown in FIG.
- the through-hole 5 gradually increases in diameter as it goes from both main surfaces of the aluminum base 3 to the inside of the through-hole 5 in a cross section parallel to the axial direction of the through-hole 5. It has a shape with a maximum diameter Ra inside the through hole 5.
- the through hole 5 has a minimum diameter Rb on one main surface side of the aluminum base 3.
- the ratio Rb / Ra between the maximum diameter Ra and the minimum diameter Rb in one through hole 5 satisfies 1> Rb / Ra ⁇ 0.1.
- the angles ⁇ 1 and ⁇ 2 formed by the main surface of the aluminum base 3 and the inner wall surface of the through hole 5 are both less than 90 °.
- This through hole 5 is the through hole A in the present invention.
- the average opening diameter of the through holes is 0.1 ⁇ m or more and less than 100 ⁇ m, and the shape has the maximum diameter Ra inside, and the maximum diameter Ra and the minimum diameter Rb are 1> Rb / Ra.
- the through-hole A has a shape satisfying ⁇ 0.1. Since the average opening diameter of the through holes is small, it is possible to prevent unevenness corresponding to the through holes from being formed on the surface of the applied active material, or to pass through, and the active material can be applied uniformly.
- the through hole A has a shape satisfying a maximum diameter Ra and a ratio of 1> Rb / Ra ⁇ 0.1 with respect to the minimum diameter Rb, as shown in FIG. Since the active material filled in is locked in the through hole, the adhesion between the active material and the aluminum plate is increased, and the active material can be prevented from falling off. Therefore, it is possible to prevent the active material from dropping and the charge / discharge capacity from decreasing.
- the angles ⁇ 1 and ⁇ 2 formed by the inner wall surface of the through hole A and the main surface of the aluminum plate are less than 90 °, but the present invention is not limited to this, and the angles ⁇ 1 and ⁇ 2 may be 90 ° or more.
- the active material can be suitably locked by the through-hole, and the active material can be prevented from falling off.
- the productivity may decrease.
- angles ⁇ 1 and ⁇ 2 are preferably less than 90 °, more preferably 5 ° to 85 °, and more preferably 35 ° to 55 °. ° is particularly preferred. Note that the angles ⁇ 1 and ⁇ 2 may be different angles or the same angle.
- the through hole A has a shape with the minimum diameter Rb on the main surface of the aluminum plate.
- the shape is not limited to this, and the shape has the minimum diameter Rb inside the through hole A. Also good.
- the shape having the minimum diameter Rb on the main surface the active material can be suitably locked by the through-hole, and the active material can be prevented from falling off. Therefore, from the viewpoints of adhesion to the active material, productivity, and the like, it is preferable that the shape has a minimum diameter Rb on at least one of the main surfaces of the aluminum plate.
- the through hole A has a shape in which the hole diameter gradually increases from both main surfaces of the aluminum base material 3 toward the inside of the through hole 5, but is not limited thereto.
- the shape may be increased after the hole diameter is once reduced toward the inside.
- the through hole A has a shape in which the hole diameter gradually increases from both main surfaces of the aluminum base 3 toward the inside of the through hole 5. Is preferred.
- the ratio of the maximum diameter Ra to the minimum diameter Rb is preferably 0.8 ⁇ Rb / Ra ⁇ 0.1, 0 .7 ⁇ Rb / Ra ⁇ 0.2 is more preferable.
- the average opening diameter of the through holes is preferably more than 5 ⁇ m and less than 80 ⁇ m, more preferably more than 5 ⁇ m and less than 40 ⁇ m, more preferably from 10 ⁇ m to 30 ⁇ m, from the viewpoints of coating properties of the active material, adhesion to the active material, and tensile strength. Is particularly preferred.
- the average opening diameter of the through-hole is obtained by photographing the surface of the aluminum plate at a magnification of 200 times from one surface of the aluminum plate using a high resolution scanning electron microscope (SEM). At least 20 through-holes that are connected in a ring shape are extracted, their opening diameters are read, and the average value of these is calculated as the average opening diameter.
- the opening diameter measured the maximum value of the distance between the edge parts of a through-hole part. That is, since the shape of the opening of the through hole is not limited to a substantially circular shape, when the shape of the opening is non-circular, the maximum value of the distance between the end portions of the through hole is the opening diameter. Therefore, for example, even in the case of a through hole having a shape in which two or more through holes are integrated, this is regarded as one through hole, and the maximum value of the distance between the end portions of the through hole portion is set as the opening diameter. .
- the shape of the through hole is a shape when seen in a cross section in the direction measured as the maximum value when measuring the opening diameter, and the maximum diameter Ra and the minimum diameter Rb are obtained by cutting the through hole with a microtome.
- a cross section is formed, and this cross section is photographed with a high resolution scanning electron microscope (SEM) at a magnification of 800 times, and 10 through holes A having a maximum diameter inside are extracted, and the maximum diameter Ra and The minimum diameter Rb is measured, and each Rb / Ra is calculated.
- SEM scanning electron microscope
- the ratio of the number of through holes A having the above shape with respect to all the through holes is not particularly limited, but is 30% or more from the viewpoint of adhesion to the active material, productivity, cost, strength of the aluminum plate, and the like. Is preferable, 30% to 90% is more preferable, and 40% to 70% is particularly preferable.
- the ratio of the through-hole A is the same as the measurement of the said average opening diameter and the measurement of the shape of the said through-hole about all the through-holes in the range of 5 mm x 5 mm, and ten places, and the number of the through-holes A Calculate the percentage of.
- the average aperture ratio of the aluminum plate is not particularly limited, but is preferably 1% to 40%, more preferably 5% to 30%, and more preferably 5% to 25% from the viewpoints of applicability, adhesion, and tensile strength. Is particularly preferred.
- the average aperture ratio was obtained by photographing the surface of the aluminum plate from directly above at a magnification of 200 times using a high-resolution scanning electron microscope (SEM), and for 30 mm ⁇ 30 mm fields (5 locations) of the obtained SEM photograph. Then, binarize with image analysis software, etc., and observe the through-hole part and the non-through-hole part. From the total opening area of the through-hole and the area of the visual field (geometric area), the ratio (opening area / geometric Area) and the average value in each field of view (5 locations) is calculated as the average aperture ratio.
- SEM scanning electron microscope
- the aluminum plate of the present invention may have non-through holes with an average opening diameter of 0.1 ⁇ m to 100 ⁇ m, that is, recesses, for the reason that the adhesion to the active material layer is further improved. .
- the recess By having the recess, the surface area is increased, and the area that is in close contact with the active material layer is increased, whereby the adhesion is further improved.
- the average opening diameter of the recesses was obtained by photographing the surface of the aluminum plate at a magnification of 2000 times from directly above using a high-resolution scanning electron microscope (SEM). At least 30 recesses (pits) having a concavo-convex structure were extracted, and the maximum diameter was read as the opening diameter, and the average value of these was calculated as the average opening diameter.
- the maximum diameter means the maximum value of the linear distances between one ridge and the other ridge constituting the opening of the recess.
- the recess is circular, it means the diameter, and the recess is elliptical. Is the major axis, and when the recess has a shape in which a plurality of circles are overlapped, it is the maximum value of the linear distance between the ridges of one circle and the ridges of another circle.
- the average opening diameter of the recesses is preferably 0.1 ⁇ m to 100 ⁇ m, and more preferably 1 ⁇ m to 50 ⁇ m.
- the density of the recesses is preferably 1000 / mm 2 to 500000 / mm 2 , more preferably 5000 / mm 2 to 300000 / mm 2 .
- the shortest pitch between the recesses is preferably 0.01 ⁇ m to 10 ⁇ m, and preferably 0.05 ⁇ m to 5 ⁇ m.
- FIG. 3 is a schematic cross-sectional view showing another example of the aluminum plate of the present invention.
- the aluminum plate 10 shown in FIG. 3 includes a first metal layer 6 and a second metal layer 6 made of a metal or alloy other than aluminum on the front and back surfaces of the aluminum base 3 having through holes and the inner surface (inner wall) of the through holes 5.
- the metal layer 7 is provided.
- the average opening diameter of the through hole can be suitably adjusted to a small range of about 0.1 ⁇ m to 20 ⁇ m.
- a metal layer can be formed by a metal coating process described later.
- the metal layer is formed on the front and back surfaces of the aluminum base 3 and the inner surface of the through hole 5.
- the present invention is not limited to this, and at least a metal is formed on the inner surface of the through hole 5.
- a layer may be formed.
- the aluminum substrate is not particularly limited, and for example, known aluminum substrates such as alloy numbers 1085, 1N30, and 3003 described in JIS standard H4000 can be used.
- the aluminum substrate is an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements.
- the thickness of the aluminum substrate is not particularly limited, but is preferably 5 ⁇ m to 1000 ⁇ m, more preferably 5 ⁇ m to 100 ⁇ m, and particularly preferably 10 ⁇ m to 30 ⁇ m.
- Active material layer There is no limitation in particular as an active material layer, The well-known active material layer used in the conventional electrical storage device can be utilized. Specifically, regarding an active material and a conductive material, a binder, a solvent, and the like that may be contained in the active material layer when an aluminum plate is used as a positive electrode current collector, JP 2012-216513 A The materials described in the paragraphs [0077] to [0088] can be adopted as appropriate, the contents of which are incorporated herein by reference. In addition, as an active material when an aluminum plate is used as a negative electrode current collector, the materials described in paragraph [0089] of JP2012-216513A can be appropriately employed, and the contents thereof are described in this specification. Incorporated into the book as a reference.
- An electrode using the aluminum plate of the present invention as a current collector can be used as a positive electrode or a negative electrode of an electricity storage device.
- the materials and applications described in paragraphs [0090] to [0123] of JP2012-216513A are appropriately used. Which is incorporated herein by reference.
- the aluminum plate of the present invention can be used for other purposes.
- it can be suitably used for heat resistant fine particle filters, sound absorbing materials, and the like.
- the method for producing an aluminum plate is a method for producing an aluminum plate having an aluminum substrate having a plurality of through holes penetrating in the thickness direction, A film forming step of forming a film mainly composed of aluminum hydroxide on the surface of the aluminum substrate; A through hole forming step of forming a through hole by performing a through hole forming process after the film forming step; After the through hole forming step, a film removing step for removing the aluminum hydroxide film, It is a manufacturing method of the aluminum plate which has this.
- the average opening diameter is 0.1 ⁇ m or more and less than 100 ⁇ m, and the shape has the maximum diameter Ra inside, and the maximum diameter Ra Since the through-hole A having a shape satisfying 1> Rb / Ra ⁇ 0.1 with the minimum diameter Rb can be formed, the coating property of the active material and the adhesion between the active material and the aluminum plate are good.
- An aluminum plate that can be suitably used for the current collector can be manufactured.
- FIGS. 4 (A) to 4 (E) and FIGS. 5 (A) to 5 (E) are schematic cross-sectional views showing an example of a preferred embodiment of a method for producing an aluminum plate.
- the manufacturing method of the aluminum plate is one main surface of the aluminum substrate 1 (the embodiment shown in FIG. 5).
- a film forming process is performed on both main surfaces to form an aluminum hydroxide film 2 (FIGS. 4A, 4 B, 5 A, and 5 B).
- An aluminum plate 10 made of an aluminum base 3 having Seisuru film removal step (Fig. 4 (C) and FIG. 4 (D), the FIG. 5 (C) and FIG. 5 (D)) is a manufacturing method having a, a.
- the manufacturing method of an aluminum plate performs an electrochemical roughening process to the aluminum base material 3 which has a through-hole after a film removal process, and produces the roughening process which produces the aluminum plate 10 which roughened the surface. It is preferable to have a process (FIGS. 4D and 4E, FIG. 5D and FIG. 5E).
- the aluminum hydroxide film has a higher resistivity than the aluminum base material. Therefore, the through holes formed in the aluminum base material by electrolytic dissolution treatment are formed in a shape in which the current is diffused more in the inner region than in the region in contact with the aluminum hydroxide film, and the inner diameter becomes the maximum diameter Ra. Is done.
- the average opening diameter is 0.1 ⁇ m or more and less than 100 ⁇ m by performing electrolytic dissolution treatment in the through hole forming step to form the through hole, and the maximum inside A through-hole having a shape with a diameter Ra and having a maximum diameter Ra and a minimum diameter Rb satisfying 1> Rb / Ra ⁇ 0.1 can be formed.
- the film formation process which the manufacturing method of an aluminum plate has is a process of giving a film formation process to the surface of an aluminum base material, and forming an aluminum hydroxide film.
- the said film formation process is not specifically limited, For example, the process similar to the formation process of a conventionally well-known aluminum hydroxide film can be given.
- As the film forming treatment for example, conditions and apparatuses described in paragraphs [0013] to [0026] of JP 2011-201123 A can be appropriately employed.
- the conditions for the film formation treatment vary depending on the electrolyte used, and thus cannot be determined unconditionally.
- the electrolyte concentration is 1 to 80% by mass
- the solution temperature is 5 to 70 ° C.
- the current density is 0.5 to 60 A / dm 2
- the voltage is 1 to 100 V
- the electrolysis time is 1 second to 20 minutes, which are adjusted to obtain a desired coating amount.
- electrochemical treatment is preferably performed using nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, or a mixed acid of two or more of these acids as the electrolytic solution.
- a direct current may be applied between the aluminum substrate and the counter electrode, or an alternating current may be applied.
- direct current is applied to the aluminum substrate, the current density is preferably 1 to 60 A / dm 2 , and more preferably 5 to 50 A / dm 2 .
- the electrochemical treatment is continuously performed, it is preferably performed by a liquid power feeding method in which power is supplied to the aluminum base material through an electrolytic solution.
- the amount of the aluminum hydroxide film formed by the film forming treatment is preferably 0.05 to 50 g / m 2 , more preferably 0.1 to 10 g / m 2 .
- a through-hole formation process is a process of performing an electrolytic dissolution process after a membrane
- the electrolytic dissolution treatment is not particularly limited, and direct current or alternating current can be used, and an acidic solution can be used as the electrolytic solution.
- the acidic solution as the electrolytic solution includes, in addition to the above acids, U.S. Pat. Nos. 4,671,859, 4,661,219, 4,618,405, 4,600,482, 4,566,960, 4,566,958, 4,566,959, 4,416,972, 4,374,710 Nos. 4,336,113 and 4,184,932, etc., can also be used.
- the concentration of the acidic solution is preferably from 0.1 to 2.5% by mass, particularly preferably from 0.2 to 2.0% by mass.
- the liquid temperature of the acidic solution is preferably 20 to 80 ° C., more preferably 30 to 60 ° C.
- the aqueous solution mainly composed of the acid is an acid aqueous solution having a concentration of 1 to 100 g / L, a nitrate compound having nitrate ions such as aluminum nitrate, sodium nitrate or ammonium nitrate, or hydrochloric acid such as aluminum chloride, sodium chloride or ammonium chloride.
- a sulfuric acid compound having a sulfate ion such as a hydrochloric acid compound having an ion, aluminum sulfate, sodium sulfate, or ammonium sulfate can be added and used in a range from 1 g / L to saturation.
- the metal contained in aluminum alloys such as iron, copper, manganese, nickel, titanium, magnesium, a silica, may melt
- a direct current is mainly used, but when an alternating current is used, the alternating current power wave is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave, etc. are used. Among these, a rectangular wave or a trapezoidal wave is preferable, and a trapezoidal wave is particularly preferable.
- an average opening diameter of 0.1 ⁇ m or more and less than 100 ⁇ m can be easily obtained by an electrochemical dissolution treatment (hereinafter also referred to as “nitric acid dissolution treatment”) using an electrolytic solution mainly composed of nitric acid.
- a through-hole having the maximum diameter Ra can be formed.
- the nitric acid dissolution treatment uses direct current, the average current density is 5 A / dm 2 or more, and the amount of electricity is 50 C / dm 2 or more because it is easy to control the dissolution point of through-hole formation. It is preferable that the electrolytic treatment is performed in step (b).
- the average current density is preferably 100 A / dm 2 or less, and the quantity of electricity is preferably 10,000 C / dm 2 or less.
- concentration and temperature of the electrolytic solution in nitric acid electrolysis are not particularly limited, and electrolysis is performed at a high concentration, for example, 30 to 60 ° C. using a nitric acid electrolytic solution having a nitric acid concentration of 15 to 35% by mass, Electrolysis can be performed at a high temperature, for example, 80 ° C. or higher, using a 7 to 2 mass% nitric acid electrolyte. Further, electrolysis can be performed using an electrolytic solution obtained by mixing at least one of sulfuric acid, oxalic acid, and phosphoric acid having a concentration of 0.1 to 50% by mass with the nitric acid electrolytic solution.
- an average opening diameter of 1 ⁇ m or more and less than 100 ⁇ m can be easily obtained by an electrochemical dissolution process (hereinafter also referred to as “hydrochloric acid dissolution process”) using an electrolytic solution mainly composed of hydrochloric acid.
- a through hole having the maximum diameter Ra can be formed.
- the hydrochloric acid dissolution treatment uses direct current, the average current density is 5 A / dm 2 or more, and the amount of electricity is 50 C / dm 2 or more because it is easy to control the dissolution point of through-hole formation. It is preferable that the electrolytic treatment is performed in step (b).
- the average current density is preferably 100 A / dm 2 or less, and the quantity of electricity is preferably 10,000 C / dm 2 or less.
- concentration and temperature of the electrolytic solution in hydrochloric acid electrolysis are not particularly limited, and electrolysis is performed at 30 to 60 ° C. using a hydrochloric acid electrolytic solution having a high concentration, for example, a hydrochloric acid concentration of 10 to 35% by mass, or a hydrochloric acid concentration of 0. Electrolysis can be performed at a high temperature, for example, 80 ° C. or higher, using a 7-2 mass% hydrochloric acid electrolyte. Further, electrolysis can be performed using an electrolytic solution obtained by mixing at least one of sulfuric acid, oxalic acid, and phosphoric acid having a concentration of 0.1 to 50% by mass with the hydrochloric acid electrolytic solution.
- the film removal step is a step of removing the aluminum hydroxide film by performing chemical dissolution treatment.
- the said film removal process can remove an aluminum hydroxide film
- the dissolution treatment is a treatment for dissolving the aluminum hydroxide film using a solution that preferentially dissolves aluminum hydroxide over aluminum (hereinafter referred to as “aluminum hydroxide solution”).
- the aluminum hydroxide solution for example, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, chromium compound, zirconium compound, titanium compound, lithium salt, cerium salt, magnesium salt, sodium silicofluoride, fluoride
- An aqueous solution containing at least one selected from the group consisting of zinc, manganese compounds, molybdenum compounds, magnesium compounds, barium compounds and halogens is preferred.
- examples of the chromium compound include chromium (III) oxide and anhydrous chromium (VI) acid.
- examples of the zirconium-based compound include zircon ammonium fluoride, zirconium fluoride, and zirconium chloride.
- examples of the titanium compound include titanium oxide and titanium sulfide.
- examples of the lithium salt include lithium fluoride and lithium chloride.
- examples of the cerium salt include cerium fluoride and cerium chloride.
- examples of the magnesium salt include magnesium sulfide.
- Examples of the manganese compound include sodium permanganate and calcium permanganate.
- Examples of the molybdenum compound include sodium molybdate.
- magnesium compounds include magnesium fluoride pentahydrate.
- barium compounds include barium oxide, barium acetate, barium carbonate, barium chlorate, barium chloride, barium fluoride, barium iodide, barium lactate, barium oxalate, barium perchlorate, barium selenate, selenite.
- Examples thereof include barium, barium stearate, barium sulfite, barium titanate, barium hydroxide, barium nitrate, and hydrates thereof.
- barium oxide, barium acetate, and barium carbonate are preferable, and barium oxide is particularly preferable.
- halogen alone include chlorine, fluorine, and bromine.
- the aluminum hydroxide solution is preferably an aqueous solution containing an acid.
- the acid include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, and the like. Good.
- the acid concentration is preferably 0.01 mol / L or more, more preferably 0.05 mol / L or more, and still more preferably 0.1 mol / L or more. There is no particular upper limit, but generally it is preferably 10 mol / L or less, more preferably 5 mol / L or less.
- the dissolution treatment is performed by bringing the aluminum base material on which the aluminum hydroxide film is formed into contact with the above-described solution.
- the method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.
- the dipping method is a treatment in which an aluminum base material on which an aluminum hydroxide film is formed is dipped in the above-described solution. Stirring during the dipping process is preferable because a uniform process is performed.
- the dipping treatment time is preferably 10 minutes or longer, more preferably 1 hour or longer, and further preferably 3 hours or longer and 5 hours or longer.
- the alkali etching treatment is a treatment for dissolving the surface layer by bringing the aluminum hydroxide film into contact with an alkali solution.
- Examples of the alkali used in the alkaline solution include caustic alkali and alkali metal salts.
- examples of the caustic alkali include sodium hydroxide (caustic soda) and caustic potash.
- Examples of the alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate, and potassium silicate; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium aluminate and alumina.
- Alkali metal aluminates such as potassium acid; alkali metal aldones such as sodium gluconate and potassium gluconate; dibasic sodium phosphate, dibasic potassium phosphate, tribasic sodium phosphate, tertiary potassium phosphate, etc.
- An alkali metal hydrogen phosphate is mentioned.
- a caustic alkali solution and a solution containing both a caustic alkali and an alkali metal aluminate are preferable from the viewpoint of high etching rate and low cost.
- an aqueous solution of sodium hydroxide is preferred.
- the concentration of the alkaline solution is preferably from 0.1 to 50% by mass, more preferably from 0.2 to 10% by mass.
- the concentration of aluminum ions is preferably 0.01 to 10% by mass, and more preferably 0.1 to 3% by mass.
- the temperature of the alkaline solution is preferably 10 to 90 ° C.
- the treatment time is preferably 1 to 120 seconds.
- Examples of the method for bringing the aluminum hydroxide film into contact with the alkaline solution include, for example, a method in which an aluminum base material on which an aluminum hydroxide film is formed is passed through a tank containing an alkali solution, and an aluminum on which an aluminum hydroxide film is formed. Examples include a method of immersing the base material in a tank containing an alkaline solution, and a method of spraying the alkaline solution onto the surface of the aluminum base material (aluminum hydroxide film) on which the aluminum hydroxide film is formed.
- an optional surface roughening treatment step that the aluminum plate production method may have is an electrochemical surface roughening treatment (hereinafter referred to as “electrolytic surface treatment”) on the aluminum substrate from which the aluminum hydroxide film has been removed.
- electrolytic surface treatment an electrochemical surface roughening treatment
- This is a step of roughening the surface or back surface of the aluminum substrate.
- electrolytic surface-roughening treatment for example, conditions and apparatuses described in paragraphs [0041] to [0050] of JP2012-216513A can be appropriately employed.
- a concave portion is also formed when the through hole is formed. Can be formed.
- the structure which performs a roughening process after forming a through-hole it is not limited to this, It is good also as a structure which forms a through-hole after a roughening process.
- a concave portion having an average opening diameter of 0.5 ⁇ m to 3.0 ⁇ m can be easily formed by an electrochemical surface roughening treatment (hereinafter also referred to as “nitric acid electrolysis”) using an electrolytic solution mainly composed of nitric acid. It can be formed at a density of 10 pieces / 100 ⁇ m 2 or more.
- nitric acid electrolysis uses an alternating current for the reason that it is possible to form a uniform and high-density recess, and the peak current density is 30 A / dm 2 or more, the average current density is 13 A / dm 2 or more, and The electrolytic treatment is preferably performed under the condition that the amount of electricity is 150 C / dm 2 or more.
- the peak current density is preferably 100 A / dm 2 or less, the average current density is preferably 40 A / dm 2 or less, and the amount of electricity is preferably 400 C / dm 2 or less.
- the concentration and temperature of the electrolytic solution in nitric acid electrolysis are not particularly limited, and electrolysis is performed at a high concentration, for example, 30 to 60 ° C. using a nitric acid electrolytic solution having a nitric acid concentration of 15 to 35% by mass, or a nitric acid concentration of 0. Electrolysis can be performed at a high temperature, for example, at 80 ° C. or higher, using a 7-2 mass% nitric acid electrolyte.
- a concave portion having an average opening diameter of 0.5 ⁇ m to 3.0 ⁇ m is formed by an electrochemical surface roughening treatment (hereinafter also referred to as “hydrochloric acid electrolysis”) using an electrolytic solution mainly composed of hydrochloric acid. It can be formed at a density of not less than 100 / ⁇ m 2 .
- the peak current density is 30 A / dm 2 or more, the average current density is 13 A / dm 2 or more, and
- the electrolytic treatment is preferably performed under the condition that the amount of electricity is 150 C / dm 2 or more.
- the peak current density is preferably 100 A / dm 2 or less, the average current density is preferably 40 A / dm 2 or less, and the amount of electricity is preferably 400 C / dm 2 or less.
- the aluminum plate manufacturing method can adjust the average opening diameter of the through holes formed by the above-described electrolytic dissolution treatment to a small range of about 0.1 ⁇ m to 20 ⁇ m. It is preferable to have a metal coating step of coating a part or all of the surface of the aluminum substrate including at least the inner wall of the through hole with a metal other than aluminum.
- “at least part or all of the surface of the aluminum substrate including the inner wall of the through hole is coated with a metal other than aluminum” means that at least the entire surface of the aluminum substrate including the inner wall of the through hole is penetrated. This means that the inner wall of the hole is covered, and the surface other than the inner wall may not be covered, or may be partially or entirely covered.
- the metal coating process will be described below with reference to FIG.
- the aluminum plate 10 shown in FIG. 3 includes the first metal layer 6 and the second metal made of a metal or alloy other than aluminum on the front and back surfaces of the aluminum base 3 having through holes and the inner wall of the through holes. It is an embodiment having the layer 7 and can be produced by, for example, performing a substitution treatment and a plating treatment described later on the aluminum base shown in FIG. 4D or FIG.
- the replacement treatment is a treatment in which zinc or a zinc alloy is subjected to replacement plating on a part or all of the surface of the aluminum substrate including at least the inner wall of the through hole.
- the displacement plating solution include a mixed solution of sodium hydroxide 120 g / l, zinc oxide 20 g / l, crystalline ferric chloride 2 g / l, lossel salt 50 g / l, and sodium nitrate 1 g / l.
- Commercially available Zn or Zn alloy plating solution may also be used.
- Substar Zn-1, Zn-2, Zn-3, Zn-8, Zn-10, Zn-111 manufactured by Okuno Pharmaceutical Co., Ltd. Zn-222, Zn-291, etc. can be used.
- the immersion time of the aluminum substrate in such a displacement plating solution is preferably 15 seconds to 40 seconds, and the immersion temperature is preferably 15 seconds to 40 seconds.
- ⁇ Plating treatment> When the zinc film is formed by replacing the surface of the aluminum base material with zinc or a zinc alloy by the above-described replacement treatment, for example, the zinc film is replaced with nickel by electroless plating described later, and then described later. It is preferable to perform a plating treatment for depositing various metals by electrolytic plating.
- the nickel plating solution used for the electroless plating treatment commercially available products can be widely used. Examples thereof include an aqueous solution containing 30 g / l nickel sulfate, 20 g / l sodium hypophosphite, and 50 g / l ammonium citrate.
- the nickel alloy plating solution include a Ni—P alloy plating solution in which a phosphorus compound is a reducing agent and a Ni—B plating solution in which a boron compound is a reducing agent.
- the immersion time in such a nickel plating solution or nickel alloy plating solution is preferably 15 seconds to 10 minutes, and the immersion temperature is preferably 30 ° C. to 90 ° C.
- a plating solution for electroplating Cu includes, for example, Cu 60 to 110 g / L, sulfuric acid 160 to 200 g / L and hydrochloric acid 0.1 to 0.15 mL / L to pure water. Furthermore, plating solutions containing Top Lucina SF Base WR 1z 5 to 5.0 mL / L, Top Lucina SF-B 0.5 to 2.0 mL / L, and Top Lucina SF Leveler 3.0 to 10 mL / L as additives are also listed. It is done.
- the immersion time in such a copper plating solution is not particularly limited because it depends on the thickness of the Cu film, but for example, when a 2 ⁇ m Cu film is applied, it is preferable to immerse for about 5 minutes at a current density of 2 A / dm,
- the immersion temperature is preferably 20 ° C. to 30 ° C.
- washing treatment it is preferable to carry out water washing after completion of the above-described processes.
- pure water, well water, tap water, or the like can be used.
- a nip device may be used to prevent the processing liquid from being brought into the next process.
- Example 1 ⁇ Preparation of current collector aluminum plate>
- the surface of an aluminum substrate JIS H-4160, alloy number: 1N30-H, aluminum purity: 99.30%) having an average thickness of 20 ⁇ m and a size of 200 mm ⁇ 300 mm is subjected to the following treatment.
- An aluminum plate was produced.
- A1 Aluminum hydroxide film formation treatment (film formation process) Using an electrolytic solution kept at 50 ° C. (nitric acid concentration 1%, sulfuric acid concentration 0.2%, aluminum concentration 0.5%), the above aluminum base material as a cathode, and the total amount of electricity is 1000 C / dm 2
- the aluminum hydroxide film was formed on the aluminum substrate.
- the electrolytic treatment was performed with a DC power source. Current density was 50A / dm 2. After the aluminum hydroxide film was formed, it was washed with water by spraying.
- Electrolytic dissolution treatment (through hole forming step) Next, using an electrolytic solution (nitric acid concentration 1%, sulfuric acid concentration 0.2%, aluminum concentration 0.5%) kept at 50 ° C., with the aluminum substrate as the anode, the total amount of electricity is 1000 C / dm 2 . Electrolytic treatment was performed below to form through holes in the aluminum base and the aluminum hydroxide film. The electrolytic treatment was performed with a DC power source. Current density was 25A / dm 2. After formation of the through hole, it was washed with water by spraying and dried.
- (C1) Aluminum hydroxide film removal treatment (film removal step) Next, the aluminum base material after the electrolytic dissolution treatment was immersed in an aqueous solution (liquid temperature 35 ° C.) having a sodium hydroxide concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% for 30 seconds, and then a sulfuric acid concentration of 30%. The aluminum hydroxide film was dissolved and removed by immersing in an aqueous solution (liquid temperature 50 ° C.) having an aluminum ion concentration of 0.5 mass% for 20 seconds. Then, the aluminum plate which has a through-hole was produced by performing water washing by spraying and making it dry.
- Example 2 An aluminum substrate was produced in the same manner as in Example 1 except that the electrolytic dissolution treatment shown in the following (b2) was performed instead of the electrolytic dissolution treatment shown in (b1).
- Electrolytic dissolution treatment It was the same as the electrolytic dissolution treatment shown in (b1) above, except that the current density was changed to 10 A / dm 2 and the total electric quantity was changed to 400 C / dm 2 .
- Example 3 In place of the aluminum hydroxide film forming process shown in (a1) above, the aluminum hydroxide film forming process shown in (a2) below is applied, and in place of the electrolytic dissolution process shown in (b1) above (b2) An aluminum plate was produced in the same manner as in Example 1 except that the electrolytic dissolution treatment shown in FIG.
- (A2) Aluminum hydroxide film formation treatment It was the same as the aluminum hydroxide film formation treatment shown in the above (a1) except that the current density was changed to 15 A / dm 2 and the total electric quantity was changed to 500 C / dm 2 .
- Example 4 An aluminum substrate was produced in the same manner as in Example 1 except that the electrolytic dissolution treatment shown in the following (b3) was performed instead of the electrolytic dissolution treatment shown in the above (b1).
- Electrolytic dissolution treatment It was the same as the electrolytic dissolution treatment shown in the above (b1) except that the current density was changed to 25 A / dm 2 and the total electric quantity was changed to 100 C / dm 2 .
- Example 5 An aluminum substrate was produced in the same manner as in Example 1 except that the electrolytic dissolution treatment shown in (b4) below was performed instead of the electrolytic dissolution treatment shown in (b1) above.
- Example 6 An aluminum substrate was produced in the same manner as in Example 1 except that the electrolytic dissolution treatment shown in the following (b5) was performed instead of the electrolytic dissolution treatment shown in (b1).
- Electrolytic dissolution treatment It was the same as the electrolytic dissolution treatment shown in (b1) above, except that the current density was changed to 5 A / dm 2 and the total electric quantity was changed to 1000 C / dm 2 .
- Example 7 An aluminum substrate was produced in the same manner as in Example 1 except that the electrolytic dissolution treatment shown in the following (b6) was performed instead of the electrolytic dissolution treatment shown in (b1).
- Electrolytic dissolution treatment It was the same as the electrolytic dissolution treatment shown in the above (b1) except that the current density was changed to 30 A / dm 2 and the total electric quantity was changed to 400 C / dm 2 .
- a negative resist solution (EF-100, manufactured by Shinwa Kogyo Co., Ltd.) was uniformly applied to a thickness of 10 ⁇ m with a bar coater on the same aluminum substrate as in Example 1, and dried at 80 ° C. for 10 minutes. Subsequently, a negative film mask (150 ⁇ m) having two 0.1 mm diameter holes in a 0.25 mm square was prepared. The negative film was brought into vacuum contact with one side of the aluminum layer on which the resist was laminated, and irradiated with 300 mJ / cm 2 of ultraviolet light from an ultraviolet exposure machine provided at a fixed distance from it, thereby forming a latent image on the resist layer.
- EF-100 manufactured by Shinwa Kogyo Co., Ltd.
- the other surface different from the surface on which the negative film mask was formed and adhered was exposed with 300 mJ / cm 2 of ultraviolet light without interposing the negative film mask. Subsequently, the unexposed portion was removed by developing with a 1% aqueous sodium carbonate solution at 1 minute / 30 ° C.
- a shower treatment was performed with a 2.2 mol / dm 3 FeCl 3 +1.0 mol / cm 3 HCl aqueous solution (temperature 40 ° C.) for 1 minute at a pressure of 0.15 MPa. After this, it was immediately washed with water and dried. Subsequently, the cured resist was peeled and removed. That is, a shower treatment was performed with a 3% aqueous sodium hydroxide solution (temperature: 40 ° C.) for 1 minute under the condition of 0.15 MPa. Then, it washed with water and dried and produced the aluminum plate.
- An aluminum plate having a through hole is formed by punching an aluminum substrate (JIS H-4160, alloy number: 1N30-H, aluminum purity: 99.30%) having a thickness of 50 ⁇ m and a size of 200 mm ⁇ 300 mm, with a diameter of 150 ⁇ m. Produced.
- the average opening diameter of the through-holes was obtained by photographing the surface of the aluminum plate at a magnification of 200 times from directly above using a high-resolution scanning electron microscope (SEM). At least 20 holes were extracted, the opening diameter was read, and the average value was calculated.
- SEM scanning electron microscope
- the maximum diameter Ra, minimum diameter Rb, and angles ⁇ 1 , ⁇ 2 of the through hole are formed by cutting the through hole with a microtome to form a cross section, and the cross section is magnified 800 times using a high resolution scanning electron microscope (SEM). 10 and extracting ten through holes A having the maximum diameter inside, the maximum diameter Ra, the minimum diameter Rb, and the angle ⁇ 1 formed between the inner wall surface of the through hole A and the main surface of the aluminum plate. , ⁇ 2 were measured.
- the ratio of the through-hole A with respect to all the through-holes is the same measurement as the measurement of the said average opening diameter, and the measurement of the shape of the said through-hole about all the through-holes in the range of 5 mm x 5 mm, and penetrating. The ratio of the number of holes A was calculated.
- the average opening diameter of the recess was obtained by photographing the surface of the aluminum plate at a magnification of 2000 times from directly above using a high-resolution scanning electron microscope (SEM), and extracting at least 30 recesses from the obtained SEM photograph. The opening diameter was read, and the average value was calculated.
- the density of the recesses was obtained by taking 10 SEM photographs at a magnification of 2000 times, calculating the number density by counting the number of recesses, and calculating the average value of 10 sheets. Further, the shortest pitch of the recesses was obtained by taking 10 SEM photographs at a magnification of 2000 times, measuring the shortest distance between adjacent recesses, and calculating the average value of 10 images.
- the average opening diameter of the through holes of each aluminum plate, the cross-sectional shape of the through holes (maximum diameter Ra, minimum diameter Rb, angles ⁇ 1 and ⁇ 2 ), the ratio of the through holes A, and the average opening diameter and density of the recesses Table 1 shows the measurement results of the shortest pitch.
- the through holes of the aluminum plates of Comparative Examples 1, 3 to 5 were through holes having a shape extending in one direction and having a maximum diameter Ra on one main surface side.
- the through-hole of the aluminum plate of Comparative Example 6 was a straight pipe shape.
- an active material layer was formed on both surfaces of the produced aluminum plate, and the applicability was evaluated by the presence or absence of irregularities on the surface of the active material layer.
- 100 parts by mass of an activated carbon powder having a specific surface area of 1950 m 2 / g, 10 parts by mass of acetylene black, 7 parts by mass of an acrylic binder, and 4 parts by mass of carboxymethylcellulose are added to water and dispersed. By doing this, the slurry was adjusted.
- the prepared slurry is applied on both sides of the aluminum plate on which the through-holes are formed to a total thickness of 200 ⁇ m by a die coater, dried at 120 ° C.
- a layer was formed.
- the surface of the formed active material layer is visually evaluated to see if there are irregularities, A is when there are no irregularities with a diameter of 40 ⁇ m or more, B is when irregularities with a diameter of 40 to 100 ⁇ m are seen, and irregularities with a diameter of 100 ⁇ m or more are seen.
- the case where it was made was designated as C.
- the average opening diameter of the through holes formed in the aluminum plate is 1 ⁇ m or more and less than 100 ⁇ m, and the shape has the maximum diameter Ra inside, and the maximum diameter Ra
- the coatability of the active material layer is improved and the surface uniformity is improved. It can be seen that the adhesion can be improved. Further, it can be seen from the comparison between Examples 1 and 6 and Examples 2 to 5 and 7 that the coatability is further improved by setting the average opening diameter to 40 ⁇ m or less. Moreover, from Examples 3 and 7, it can be seen that the adhesiveness is further improved by setting the shortest pitch of the recesses to 10 ⁇ m or less. From the above, the effects of the present invention are clear.
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Abstract
Description
また、特許文献2には、多数の貫通孔がエッチングにより設けられている金属箔からなる孔開き集電体が記載されており、また、集電体に活物質を塗布することが記載されている([請求項1][0002])。
また、貫通孔の径が大きいと、塗布した活物質の表面に、集電体の貫通孔に対応した凹凸ができたり、裏抜けしたりして、活物質表面の均一性が損なわれて塗布性が低下してしまう。
例えば、特許文献1には、貫通孔の内径を0.2~5μmの範囲とすることで、塗布した活物質の裏抜け等を防止することが記載されている([0032][0036])。
また、このように内壁面が傾斜した形状の貫通孔の形成方法として、特許文献2には、無孔金属箔の表面に、多数の貫通孔を有する孔開きレジスト膜を接合し、この無孔金属箔の裏面に、無孔レジスト膜を接合してなる三層積層体に、エッチングを施す方法が開示されている([0016])。
しかしながら、貫通孔の径をより微細な径にして、さらに、貫通孔の形状を上記のような一方の面から他方の面に向かって拡大する形状とした場合でも、活物質とアルミニウム板との密着性が十分でないということがわかった。
また、特許文献2に記載される貫通孔の開口径は、0.1mm~3mmであり、特許文献2に記載の方法では、より微細な径で、内壁面が傾斜した形状の貫通孔を形成することが困難であった。
すなわち、以下の構成により上記目的を達成することができることを見出した。
貫通孔の平均開口径が0.1μm以上100μm未満であり、
内部で最大径Raとなる形状であり、最大径Raと最小径Rbとが1>Rb/Ra≧0.1を満たす形状の貫通孔Aを有するアルミニウム板。
[2] アルミニウム板の主面と貫通孔Aの内壁面とのなす角度が90°未満である[1]に記載のアルミニウム板。
[3] アルミニウム板の主面と貫通孔Aの内壁面とのなす角度が5~85°である[1]または[2]に記載のアルミニウム板。
[4] 貫通孔Aが、アルミニウム板の主面上で最小径Rbとなる[1]~[3]のいずれかに記載のアルミニウム板。
[5] 貫通孔Aの径が、アルミニウム板の主面から内部に向かうにしたがって、漸次、大きくなる形状である[1]~[4]のいずれかに記載のアルミニウム板。
[6] 全貫通孔に対する、貫通孔Aの割合が30%以上である[1]~[5]のいずれかに記載のアルミニウム板。
[7] アルミニウム板の厚さが、5μm~100μmである[1]~[6]のいずれかに記載のアルミニウム板。
[8] アルミニウム板の主面に平均開口径が0.1μm~100μmの貫通していない凹部を有する[1]~[7]のいずれかに記載のアルミニウム板。
[9] 凹部の密度が、1000~500000個/mm2である[8]に記載のアルミニウム板。
[10] 凹部間の最短ピッチが0.01μm~10μmである[8]または[9]に記載のアルミニウム板。
[11] アルミニウム基材の表面に水酸化アルミニウムを主成分とする水酸化アルミニウム皮膜を形成する皮膜形成工程と、
皮膜形成工程の後に、貫通孔形成処理を行って貫通孔を形成する貫通孔形成工程と、
貫通孔形成工程の後に、水酸化アルミニウム皮膜を除去する皮膜除去工程とを有するアルミニウム板の製造方法。
[12] 皮膜形成工程は、硝酸、塩酸、硫酸、燐酸、シュウ酸、あるいは、これらの2以上の混酸を用いて電気化学的処理を行って、水酸化アルミニウム皮膜を形成する[11]に記載のアルミニウム板の製造方法。
[13] 貫通孔形成工程は、硝酸、塩酸、硫酸、燐酸、シュウ酸、あるいは、これらの2以上の混酸を用いて電気化学的溶解処理を行って、貫通孔を形成する[11]または[12]に記載のアルミニウム板の製造方法。
[14] 皮膜除去工程は、硝酸、塩酸、硫酸、燐酸、シュウ酸、あるいは、これらの2以上の混酸、または、水酸化ナトリウムを用いて化学的溶解処理を行って、水酸化アルミニウム皮膜を除去する[11]~[13]のいずれかに記載のアルミニウム板の製造方法。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本発明のアルミニウム板は、厚み方向に貫通する複数の貫通孔を有するアルミニウム板であって、貫通孔の平均開口径が0.1μm以上100μm未満であり、内部で最大径Raとなる形状であり、最大径Raと最小径Rbとが1>Rb/Ra≧0.1を満たす形状の貫通孔Aを有するアルミニウム板である。
次に、本発明のアルミニウム板の構成について、図1(A)~図1(C)を用いて説明する。
図1(A)および図1(B)に示すように、アルミニウム板10は、アルミニウム基材3に、厚さ方向に貫通する貫通孔5を複数、形成してなるものである。
また、図1(C)に示す電極30は、図1(B)に示すアルミニウム板10の両方の主面に活物質層32が積層されてなるものである。図に示すように、活物質層32は貫通孔5中にも充填されており、両面に形成される活物質層32と一体化されている。
図2は、図1(A)に示すアルミニウム板10の貫通孔5を拡大して示す断面図である。
図2に示すように、貫通孔5は、貫通孔5の軸方向に平行な断面において、アルミニウム基材3の両主面から貫通孔5の内部に向かうにしたがって、漸次、孔径が大きくなり、貫通孔5の内部で最大径Raとなる形状を有する。従って、貫通孔5は、アルミニウム基材3の一方の主面側で最小径Rbとなる。
また、1つの貫通孔5における最大径Raと最小径Rbとの比率Rb/Raは、1>Rb/Ra≧0.1を満たす。
また、図に示す貫通孔5は、アルミニウム基材3の主面と貫通孔5の内壁面とのなす角度θ1およびθ2が共に、90°未満である。
この貫通孔5は、本発明における貫通孔Aである。
一方で、アルミニウム板に、活物質を塗布した場合、アルミニウム板と活物質との密着性が弱くなるという問題があり、特に、貫通孔を微細に形成した場合に、アルミニウム板と活物質との密着性が弱くなって、活物質が脱落しやすいという問題があった。
貫通孔の平均開口径が小さいので、塗布した活物質の表面に、貫通孔に対応した凹凸ができたり、裏抜けしたりすることを防止でき、活物質を均一に塗布することができる。また、内部で最大径Raとなり、最小径Rbとの比が1>Rb/Ra≧0.1を満たす形状の貫通孔Aを有するので、図1(C)に示すように、貫通孔の内部に充填された活物質が貫通孔に係止されるため、活物質とアルミニウム板との密着性が高くなり、活物質の脱落を防止できる。従って、活物質が脱落して、放充電容量が低下することを防止できる。
従って、活物質との密着性、生産性、コスト、アルミニウム板の強度等の観点から、角度θ1およびθ2は、90°未満が好ましく、5°~85°がより好ましく、35°~55°が特に好ましい。
なお、角度θ1およびθ2は、それぞれ異なる角度であっても良いし、同じ角度であってもよい。
従って、活物質との密着性、生産性等の観点から、アルミニウム板の主面の少なくとも一方で最小径Rbとなる形状であるのが好ましい。
しかしながら、活物質との密着性、生産性等の観点から、貫通孔Aは、アルミニウム基材3の両主面から貫通孔5の内部に向かうにしたがって、漸次、孔径が大きくなる形状であるのが好ましい。
従って、活物質との密着性、生産性、コスト、アルミニウム板の強度等の観点から、最大径Raと最小径Rbとの比は、0.8≧Rb/Ra≧0.1が好ましく、0.7≧Rb/Ra≧0.2がより好ましい。
なお、開口径は、貫通孔部分の端部間の距離の最大値を測定した。すなわち、貫通孔の開口部の形状は略円形状に限定はされないので、開口部の形状が非円形状の場合には、貫通孔部分の端部間の距離の最大値を開口径とする。従って、例えば、2以上の貫通孔が一体化したような形状の貫通孔の場合にも、これを1つの貫通孔とみなし、貫通孔部分の端部間の距離の最大値を開口径とする。
なお、貫通孔Aの割合は、5mm×5mmの範囲、10箇所における全貫通孔について、上記平均開口径の測定、および、上記貫通孔の形状の測定と同じ測定を行い、貫通孔Aの数の割合を算出する。
凹部を有することにより、表面積が増加し、活物質層と密着する面積が増加することで、密着性がより向上する。
また、密着性の観点から、凹部の密度は、1000個/mm2~500000個/mm2であるのが好ましく、5000個/mm2~300000個/mm2であるのがより好ましい。
また、密着性の観点から、凹部間の最短ピッチは、0.01μm~10μmであるのが好ましく、0.05μm~5μmであるのが好ましい。
図3は、本発明のアルミニウム板の他の一例を示す模式的な断面図である。
図3に示すアルミニウム板10は、貫通孔を有するアルミニウム基材3の表面および裏面ならびに貫通孔5の内表面(内壁)にアルミニウム以外の金属または合金からなる第1の金属層6および第2の金属層7を有する態様である。
このように、貫通孔の内表面に金属層を形成することで、貫通孔の平均開口径を0.1μm~20μm程度の小さい範囲に好適に調整できる。
このような金属層は、後述する金属被覆工程により形成することができる。
なお、図示例においては、アルミニウム基材3の表面および裏面ならびに貫通孔5の内表面に金属層を形成する構成としたが、これに限定はされず、少なくとも、貫通孔5の内表面に金属層を形成すればよい。
上記アルミニウム基材は、特に限定はされず、例えば、JIS規格H4000に記載されている合金番号1085、1N30、3003等の公知のアルミニウム基材を用いることができる。なお、アルミニウム基材は、アルミニウムを主成分とし、微量の異元素を含む合金板である。
アルミニウム基材の厚みとしては、特に限定はないが、5μm~1000μmが好ましく、5μm~100μmがより好ましく、10μm~30μmが特に好ましい。
活物質層としては特に限定はなく、従来の蓄電デバイスにおいて用いられる公知の活物質層が利用可能である。
具体的には、アルミニウム板を正極の集電体として用いる場合の、活物質および活物質層に含有していてもよい導電材、結着剤、溶媒等については、特開2012-216513号公報の[0077]~[0088]段落に記載された材料を適宜採用することができ、その内容は本明細書に参照として取り込まれる。
また、アルミニウム板を負極の集電体として用いる場合の、活物質については、特開2012-216513号公報の[0089]段落に記載された材料を適宜採用することができ、その内容は本明細書に参照として取り込まれる。
本発明のアルミニウム板を集電体として利用する電極は、蓄電デバイスの正極あるいは負極として用いることができる。
ここで、蓄電デバイス(特に、二次電池)の具体的な構成や適用される用途については、特開2012-216513号公報の[0090]~[0123]段落に記載された材料や用途を適宜採用することができ、その内容は本明細書に参照として取り込まれる。
次に、本発明のアルミニウム板の製造方法について説明する。
アルミニウム板の製造方法は、厚み方向に貫通する複数の貫通孔を有するアルミニウム基材を有するアルミニウム板の製造方法であって、
アルミニウム基材の表面に水酸化アルミニウムを主成分とする皮膜を形成する皮膜形成工程と、
皮膜形成工程の後に、貫通孔形成処理を行って貫通孔を形成する貫通孔形成工程と、
貫通孔形成工程の後に、水酸化アルミニウム皮膜を除去する皮膜除去工程と、
を有するアルミニウム板の製造方法である。
アルミニウム板の製造方法は、図4(A)~図4(E)および図5(A)~図5(E)に示すように、アルミニウム基材1の一方の主面(図5に示す態様においては両方の主面)に対して皮膜形成処理を施し、水酸化アルミニウム皮膜2を形成する皮膜形成工程(図4(A)および図4(B),図5(A)および図5(B))と、皮膜形成工程の後に電解溶解処理を施して貫通孔5を形成し、貫通孔を有するアルミニウム基材3および貫通孔を有する水酸化アルミニウム皮膜4を有するアルミニウム板を作製する貫通孔形成工程(図4(B)および図4(C),図5(B)および図5(C))と、貫通孔形成工程の後に、貫通孔を有する水酸化アルミニウム皮膜4を除去し、貫通孔を有するアルミニウム基材3からなるアルミニウム板10を作製する皮膜除去工程(図4(C)および図4(D),図5(C)および図5(D))と、を有する製造方法である。
また、アルミニウム板の製造方法は、皮膜除去工程の後に、貫通孔を有するアルミニウム基材3に電気化学的粗面化処理を施し、表面を粗面化したアルミニウム板10を作製する粗面化処理工程(図4(D)および図4(E),図5(D)および図5(E))を有しているのが好ましい。
従って、水酸化アルミニウム皮膜を形成する皮膜形成工程の後に、貫通孔形成工程において電解溶解処理を施して貫通孔を形成することで、平均開口径が0.1μm以上100μm未満であり、内部で最大径Raとなる形状であり、最大径Raと最小径Rbとが1>Rb/Ra≧0.1を満たす形状の貫通孔を形成することができる。
本発明において、アルミニウム板の製造方法が有する皮膜形成工程は、アルミニウム基材の表面に皮膜形成処理を施し、水酸化アルミニウム皮膜を形成する工程である。
上記皮膜形成処理は特に限定されず、例えば、従来公知の水酸化アルミニウム皮膜の形成処理と同様の処理を施すことができる。
皮膜形成処理としては、例えば、特開2011-201123号公報の[0013]~[0026]段落に記載された条件や装置を適宜採用することができる。
硝酸、塩酸を含む電解液中で電気化学的処理を行う場合には、アルミニウム基材と対極との間に直流を印加してもよく、交流を印加してもよい。アルミニウム基材に直流を印加する場合においては、電流密度は、1~60A/dm2であるのが好ましく、5~50A/dm2であるのがより好ましい。連続的に電気化学的処理を行う場合には、アルミニウム基材に、電解液を介して給電する液給電方式により行うのが好ましい。
貫通孔形成工程は、皮膜形成工程の後に電解溶解処理を施し、貫通孔を形成する工程である。
上記電解溶解処理は特に限定されず、直流または交流を用い、酸性溶液を電解液に用いることができる。中でも、硝酸、塩酸の少なくとも1以上の酸を用いて電気化学処理を行うのが好ましく、これらの酸に加えて硫酸、燐酸、シュウ酸の少なくとも1以上の混酸を用いて電気化学的処理を行うのが更に好ましい。
また、上記酸を主体とする水溶液には、鉄、銅、マンガン、ニッケル、チタン、マグネシウム、シリカ等のアルミニウム合金中に含まれる金属が溶解していてもよい。好ましくは、酸の濃度0.1~2質量%の水溶液にアルミニウムイオンが1~100g/Lとなるように、塩化アルミニウム、硝酸アルミニウム、硫酸アルミニウム等を添加した液を用いることが好ましい。
本発明においては、硝酸を主体とする電解液を用いた電気化学的溶解処理(以下、「硝酸溶解処理」とも略す。)により、容易に、平均開口径が0.1μm以上100μm未満で、内部で最大径Raとなる貫通孔を形成することができる。
ここで、硝酸溶解処理は、貫通孔形成の溶解ポイントを制御しやすい理由から、直流電流を用い、平均電流密度を5A/dm2以上とし、かつ、電気量を50C/dm2以上とする条件で施す電解処理であるであるのが好ましい。なお、平均電流密度は100A/dm2以下であるのが好ましく、電気量は10000C/dm2以下であるのが好ましい。
また、硝酸電解における電解液の濃度や温度は特に限定されず、高濃度、例えば、硝酸濃度15~35質量%の硝酸電解液を用いて30~60℃で電解を行ったり、硝酸濃度0.7~2質量%の硝酸電解液を用いて高温、例えば、80℃以上で電解を行うことができる。
また、上記硝酸電解液に濃度0.1~50質量%の硫酸、シュウ酸、燐酸の少なくとも1つを混ぜた電解液を用いて電解を行うことができる。
本発明においては、塩酸を主体とする電解液を用いた電気化学的溶解処理(以下、「塩酸溶解処理」とも略す。)によっても、容易に、平均開口径が1μm以上100μm未満で、内部で最大径Raとなる貫通孔を形成することができる。
ここで、塩酸溶解処理は、貫通孔形成の溶解ポイントを制御しやすい理由から、直流電流を用い、平均電流密度を5A/dm2以上とし、かつ、電気量を50C/dm2以上とする条件で施す電解処理であるであるのが好ましい。なお、平均電流密度は100A/dm2以下であるのが好ましく、電気量は10000C/dm2以下であるのが好ましい。
また、塩酸電解における電解液の濃度や温度は特に限定されず、高濃度、例えば、塩酸濃度10~35質量%の塩酸電解液を用いて30~60℃で電解を行ったり、塩酸濃度0.7~2質量%の塩酸電解液を用いて高温、例えば、80℃以上で電解を行うことができる。
また、上記塩酸電解液に濃度0.1~50質量%の硫酸、シュウ酸、燐酸の少なくとも1つを混ぜた電解液を用いて電解を行うことができる。
皮膜除去工程は、化学的溶解処理を行って水酸化アルミニウム皮膜を除去する工程である。
上記皮膜除去工程は、例えば、後述する酸エッチング処理やアルカリエッチング処理を施すことにより水酸化アルミニウム皮膜を除去することができる。
上記溶解処理は、アルミニウムよりも水酸化アルミニウムを優先的に溶解させる溶液(以下、「水酸化アルミニウム溶解液」という。)を用いて水酸化アルミニウム皮膜を溶解させる処理である。
ジルコニウム系化合物としては、例えば、フッ化ジルコンアンモニウム、フッ化ジルコニウム、塩化ジルコニウムが挙げられる。
チタン化合物としては、例えば、酸化チタン、硫化チタンが挙げられる。
リチウム塩としては、例えば、フッ化リチウム、塩化リチウムが挙げられる。
セリウム塩としては、例えば、フッ化セリウム、塩化セリウムが挙げられる。
マグネシウム塩としては、例えば、硫化マグネシウムが挙げられる。
マンガン化合物としては、例えば、過マンガン酸ナトリウム、過マンガン酸カルシウムが挙げられる。
モリブデン化合物としては、例えば、モリブデン酸ナトリウムが挙げられる。
マグネシウム化合物としては、例えば、フッ化マグネシウム・五水和物が挙げられる。
バリウム化合物としては、例えば、酸化バリウム、酢酸バリウム、炭酸バリウム、塩素酸バリウム、塩化バリウム、フッ化バリウム、ヨウ化バリウム、乳酸バリウム、シュウ酸バリウム、過塩素酸バリウム、セレン酸バリウム、亜セレン酸バリウム、ステアリン酸バリウム、亜硫酸バリウム、チタン酸バリウム、水酸化バリウム、硝酸バリウム、あるいはこれらの水和物等が挙げられる。
上記バリウム化合物の中でも、酸化バリウム、酢酸バリウム、炭酸バリウムが好ましく、酸化バリウムが特に好ましい。
ハロゲン単体としては、例えば、塩素、フッ素、臭素が挙げられる。
酸濃度としては、0.01mol/L以上であるのが好ましく、0.05mol/L以上であるのがより好ましく、0.1mol/L以上であるのが更に好ましい。上限は特にないが、一般的には10mol/L以下であるのが好ましく、5mol/L以下であるのがより好ましい。
浸せき処理の時間は、10分以上であるのが好ましく、1時間以上であるのがより好ましく、3時間以上、5時間以上であるのが更に好ましい。
アルカリエッチング処理は、上記水酸化アルミニウム皮膜をアルカリ溶液に接触させることにより、表層を溶解させる処理である。
本発明において、アルミニウム板の製造方法が有していてもよい任意の粗面化処理工程は、水酸化アルミニウム皮膜を除去したアルミニウム基材に対して電気化学的粗面化処理(以下、「電解粗面化処理」とも略す。)を施し、アルミニウム基材の表面ないし裏面を粗面化する工程である。
前述のとおり、電解粗面化処理を施し、アルミニウム基材の表面を粗面化することにより、活物質を含む層との密着性が向上するとともに、表面積が増えることによって接触面積が増えるため、本発明の製造方法により得られるアルミニウム板(集電体)を用いた蓄電デバイスの容量維持率が高くなる。
上記電解粗面化処理としては、例えば、特開2012-216513号公報の[0041]~[0050]段落に記載された条件や装置を適宜採用することができる。
また、上記実施形態では、貫通孔を形成した後に粗面化処理を行う構成としたが、これに限定はされず、粗面化処理の後に貫通孔を形成する構成としてもよい。
本発明においては、硝酸を主体とする電解液を用いた電気化学的粗面化処理(以下、「硝酸電解」とも略す。)により、容易に平均開口径0.5μm~3.0μmの凹部を10個/100μm2以上の密度で形成することができる。
ここで、硝酸電解は、均一で密度の高い凹部形成が可能となる理由から、交流電流を用い、ピーク電流密度を30A/dm2以上とし、平均電流密度を13A/dm2以上とし、かつ、電気量を150C/dm2以上とする条件で施す電解処理であるであるのが好ましい。なお、ピーク電流密度は100A/dm2以下であるのが好ましく、平均電流密度は40A/dm2以下であるのが好ましく、電気量は400C/dm2以下であるのが好ましい。
また、硝酸電解における電解液の濃度や温度は特に限定されず、高濃度、例えば、硝酸濃度15~35質量%の硝酸電解液を用いて30~60℃で電解を行ったり、硝酸濃度0.7~2質量%の硝酸電解液を用いて高温、例えば、80℃以上で電解を行ったりすることができる。
本発明においては、塩酸を主体とする電解液を用いた電気化学的粗面化処理(以下、「塩酸電解」とも略す。)によっても、平均開口径0.5μm~3.0μmの凹部を10個/100μm2以上の密度で形成することができる。
ここで、塩酸電解においては、均一で密度の高い凹部形成が可能となる理由から、交流電流を用い、ピーク電流密度を30A/dm2以上とし、平均電流密度を13A/dm2以上とし、かつ、電気量を150C/dm2以上とする条件で施す電解処理であるであるのが好ましい。なお、ピーク電流密度は100A/dm2以下であるのが好ましく、平均電流密度は40A/dm2以下であるのが好ましく、電気量は400C/dm2以下であるのが好ましい。
本発明において、アルミニウム板の製造方法は、上述した電解溶解処理により形成された貫通孔の平均開口径を0.1μm~20μm程度の小さい範囲に調整できる理由から、上述した皮膜除去工程の後に、少なくとも貫通孔の内壁を含むアルミニウム基材の表面の一部または全部をアルミニウム以外の金属で被覆する金属被覆工程を有しているのが好ましい。
ここで、「少なくとも貫通孔の内壁を含むアルミニウム基材の表面の一部または全部をアルミニウム以外の金属で被覆する」とは、貫通孔の内壁を含むアルミニウム基材の全表面のうち、少なくとも貫通孔の内壁については被覆されていることを意味しており、内壁以外の表面は、被覆されていなくてもよく、一部または全部が被覆されていてもよい。
以下に、図3を用いて、金属被覆工程を説明する。
上記置換処理は、少なくとも貫通孔の内壁を含むアルミニウム基材の表面の一部または全部に、亜鉛または亜鉛合金を置換めっきする処理である。
置換めっき液としては、例えば、水酸化ナトリウム120g/l、酸化亜鉛20g/l、結晶性塩化第二鉄2g/l、ロッセル塩50g/l、硝酸ナトリウム1g/lの混合溶液などが挙げられる。
また、市販のZnまたはZn合金めっき液を使用してもよく、例えば、奥野製薬工業株式会社製サブスターZn-1、Zn-2、Zn-3、Zn-8、Zn-10、Zn-111、Zn-222、Zn-291等を使用することができる。
このような置換めっき液へのアルミニウム基材の浸漬時間は15秒~40秒であるのが好ましく、浸漬温度は15秒~40秒であるのが好ましい。
上述した置換処理により、アルミニウム基材の表面に亜鉛または亜鉛合金を置換めっきして亜鉛皮膜を形成させた場合は、例えば、後述する無電解めっきにより亜鉛皮膜をニッケルに置換させた後、後述する電解めっきにより各種金属を析出させる、めっき処理を施すのが好ましい。
無電解めっき処理に用いるニッケルめっき液としては、市販品が幅広く使用でき、例えば、硫酸ニッケル30g/l、次亜リン酸ソーダ20g/l、クエン酸アンモニウム50g/lを含む水溶液などが挙げられる。
また、ニッケル合金めっき液としては、りん化合物が還元剤となるNi-P合金めっき液やホウ素化合物が還元剤となるNi-Bメッキ液などが挙げられる。
このようなニッケルめっき液やニッケル合金めっき液への浸漬時間は15秒~10分であるのが好ましく、浸漬温度は30℃~90℃であるのが好ましい。
電解めっき処理として、例えば、Cuを電気めっきする場合のめっき液は、例えば、硫酸Cu60~110g/L、硫酸160~200g/Lおよび塩酸0.1~0.15mL/Lを純水に加え、さらに奥野製薬株式会社製トップルチナSFベースWR1z5~5.0mL/L、トップルチナSF-B0.5~2.0mL/L及びトップルチナSFレベラー3.0~10mL/Lを添加剤として加えためっき液が挙げられる。
このような銅めっき液への浸漬時間は、Cu膜の厚さによるため特に限定されないが、例えば、2μmのCu膜をつける場合は、電流密度2A/dmで約5分間浸漬するのが好ましく、浸漬温度は20℃~30℃であるのが好ましい。
本発明においては、上述した各処理の工程終了後には水洗を行うのが好ましい。水洗には、純水、井水、水道水等を用いることができる。処理液の次工程への持ち込みを防ぐためにニップ装置を用いてもよい。
<集電体用アルミニウム板の作製>
平均厚さ20μm、大きさ200mm×300mmのアルミニウム基材(JIS H-4160、合金番号:1N30-H、アルミニウム純度:99.30%)の表面に、以下に示す処理を施し、集電体用アルミニウム板を作製した。
50℃に保温した電解液(硝酸濃度1%、硫酸濃度0.2%、アルミニウム濃度0.5%)を用いて、上記アルミニウム基材を陰極として、電気量総和が1000C/dm2の条件下で電解処理を施し、アルミニウム基材に水酸化アルミ皮膜を形成した。なお、電解処理は、直流電源で行った。電流密度は、50A/dm2とした。
水酸化アルミニウム皮膜形成後、スプレーによる水洗を行った。
次いで、50℃に保温した電解液(硝酸濃度1%、硫酸濃度0.2%、アルミニウム濃度0.5%)を用いて、アルミニウム基材を陽極として、電気量総和が1000C/dm2の条件下で電解処理を施し、アルミニウム基材及び水酸化アルミ皮膜に貫通孔を形成した。なお、電解処理は、直流電源で行った。電流密度は、25A/dm2とした。
貫通孔の形成後、スプレーによる水洗を行い、乾燥させた。
次いで、電解溶解処理後のアルミニウム基材を、水酸化ナトリウム濃度5質量%、アルミニウムイオン濃度0.5質量%の水溶液(液温35℃)中に30秒間浸漬させた後、硫酸濃度30%、アルミイオン濃度0.5質量%の水溶液(液温50℃)中に20秒間浸漬させることにより、水酸化アルミニウム皮膜を溶解し、除去した。
その後、スプレーによる水洗を行い、乾燥させることにより、貫通孔を有するアルミニウム板を作製した。
上記(b1)に示す電解溶解処理に代えて、下記(b2)に示す電解溶解処理を施した以外は、実施例1と同様にしてアルミニウム基材を作製した。
電流密度を10A/dm2、電気量総和を400C/dm2の条件に変更した以外は、上記(b1)に示す電解溶解処理と同様とした。
上記(a1)に示す水酸化アルミニウム皮膜形成処理に代えて、下記(a2)に示す水酸化アルミニウム皮膜形成処理を施し、また、上記(b1)に示す電解溶解処理に代えて、上記(b2)に示す電解溶解処理を施した以外は、実施例1と同様にしてアルミニウム板を作製した。
電流密度を15A/dm2、電気量総和を500C/dm2の条件に変更した以外は、上記(a1)に示す水酸化アルミニウム皮膜形成処理と同様とした。
上記(b1)に示す電解溶解処理に代えて、下記(b3)に示す電解溶解処理を施した以外は、実施例1と同様にしてアルミニウム基材を作製した。
電流密度を25A/dm2、電気量総和を100C/dm2の条件に変更した以外は、上記(b1)に示す電解溶解処理と同様とした。
上記(b1)に示す電解溶解処理に代えて、下記(b4)に示す電解溶解処理を施した以外は、実施例1と同様にしてアルミニウム基材を作製した。
電流密度を25A/dm2、電気量総和を800C/dm2の条件に変更した以外は、上記(b1)に示す電解溶解処理と同様とした。
上記(b1)に示す電解溶解処理に代えて、下記(b5)に示す電解溶解処理を施した以外は、実施例1と同様にしてアルミニウム基材を作製した。
電流密度を5A/dm2、電気量総和を1000C/dm2の条件に変更した以外は、上記(b1)に示す電解溶解処理と同様とした。
上記(b1)に示す電解溶解処理に代えて、下記(b6)に示す電解溶解処理を施した以外は、実施例1と同様にしてアルミニウム基材を作製した。
電流密度を30A/dm2、電気量総和を400C/dm2の条件に変更した以外は、上記(b1)に示す電解溶解処理と同様とした。
実施例1と同様のアルミニウム基材に、ネガ型レジスト液(進和工業株式会社製、EF-100)をバーコーターで10μm厚に均一塗布し、80℃で10分乾燥した。続いて、0.25mm四方に0.1mm径の孔が2つあるネガフィルムマスク(150μm)を用意した。そのネガフィルムをレジストが積層されたアルミの片面に真空密着させ、そこから一定の距離を置いて設けた紫外線露光機から300mJ/cm2の紫外線を照射し、レジスト層に潜像を形成した。一方、ネガフィルムマスクを形成密着させた面と異なる他方の面は、ネガフィルムマスクを介在させず全面を300mJ/cm2の紫外線で露光した。続いて、未露光箇所を1%炭酸ナトリウム水溶液により1分間/30℃の条件で現像することで除去した。
平均厚さ20μm、大きさ200mm×300mmのアルミニウム基材(JIS 1099-O、アルミニウム純度:99.99%)を温度75℃、濃度5%の塩酸溶液に浸漬させた状態で、電流密度が25A/dm2で直流電流を4秒間流すことによって、集電体用アルミニウム板を作製した。
アルミニウム面のエッチング除去の際のシャワー処理として、2.2mol/dm3 FeCl3+1.0mol/cm3 HCl水溶液(温度40℃)により40秒間、0.15MPaの圧力でシャワー処理を行った以外は、比較例1と同様にしてアルミニウム板を作製した。
アルミニウム面のエッチング除去の際のシャワー処理として、2.2mol/dm3 FeCl3+1.0mol/cm3 HCl水溶液(温度40℃)により20秒間、0.15MPaの圧力でシャワー処理を行った以外は、比較例1と同様にしてアルミニウム板を作製した。
アルミニウム板のB面を使用し、アルミニウム面のエッチング除去の際のシャワー処理として、2.2mol/dm3 FeCl3+1.0mol/cm3 HCl水溶液(温度40℃)により20秒間、0.15MPaの圧力でシャワー処理を行った以外は、比較例1と同様にしてアルミニウム板を作製した。
厚さ50μm、大きさ200mm×300mmのアルミニウム基材(JIS H-4160、合金番号:1N30-H、アルミニウム純度:99.30%)に直径150μmのパンチング加工を施し、貫通孔を有するアルミニウム板を作製した。
また、凹部の密度は、倍率2000倍のSEM写真を10枚撮影し、凹部の数を数えて数密度を算出し、10枚の平均値を算出して求めた。
また、凹部の最短ピッチは、倍率2000倍のSEM写真を10枚撮影し、隣接する凹部同士で最短となる距離を測定し、10枚の平均値を算出して求めた。
なお、比較例1、3~5のアルミニウム板の貫通孔は、一方向に広がる形状で一方の主面側で最大径Raとなる貫通孔であった。また、比較例6のアルミニウム板の貫通孔は、直管形状であった。
<塗布性>
作製したアルミニウム板の両面に活物質層を形成して、活物質層の表面の凹凸の有無により塗布性を評価した。
まず、活物質として、比表面積が1950m2/gの活性炭粉末100質量部と、アセチレンブラック10質量部と、アクリル系バインダー7質量部と、カルボキシメチルセルロース4質量部とを、水に添加して分散することにより、スラリーを調整した。
次に、調整したスラリーを、貫通孔が形成されたアルミニウム板の両面に、ダイコーターによって合計200μmの厚みになるように塗工し、120℃で30分間乾燥し、アルミニウム板の表面に活物質層を形成した。
形成した活物質層の表面に、凹凸が見られるかを目視評価し、直径40μm以上の凹凸が無い場合をA、直径40~100μmの凹凸が見られる場合をB、直径100μm以上の凹凸が見られる場合をCとした。
アルミニウム板の表面に活物質層を形成した後、一部をサンプリングして、JIS Z 1522:2009に基づいて、規定されたテープを用いて、剥離試験を行った。テープに、アルミニウム板から剥離した活物質の貼着が無かった場合をA、テープの一部にアルミニウム板から剥離した活物質の貼着が認められた場合をB、テープの全面にアルミニウム板から剥離した活物質の貼着が認められた場合をCとした。
評価結果を表1に示す。
また、実施例1、6と実施例2~5、7との対比から、平均開口径40μm以下とすることで塗布性がより向上することがわかる。
また、実施例3、7から、凹部の最短ピッチが10μm以下とすることで密着性がより向上することがわかる。
以上より本発明の効果は明らかである。
2 水酸化アルミニウム皮膜
3 貫通孔を有するアルミニウム基材
4 貫通孔を有する水酸化アルミニウム皮膜
5 貫通孔
6 第1の金属層
7 第2の金属層
10 アルミニウム板
30 電極
32 活物質層
Claims (14)
- 厚み方向に貫通する複数の貫通孔を有するアルミニウム板であって、
前記貫通孔の平均開口径が0.1μm以上100μm未満であり、
内部で最大径Raとなる形状であり、最大径Raと最小径Rbとが1>Rb/Ra≧0.1を満たす形状の貫通孔Aを有することを特徴とするアルミニウム板。 - 前記アルミニウム板の主面と前記貫通孔Aの内壁面とのなす角度が90°未満である請求項1に記載のアルミニウム板。
- 前記アルミニウム板の主面と前記貫通孔Aの内壁面とのなす角度が5~85°である請求項1または2に記載のアルミニウム板。
- 前記貫通孔Aが、前記アルミニウム板の主面上で最小径Rbとなる請求項1~3のいずれか1項に記載のアルミニウム板。
- 前記貫通孔Aの径が、前記アルミニウム板の主面から内部に向かうにしたがって、漸次、大きくなる形状である請求項1~4のいずれか1項に記載のアルミニウム板。
- 全貫通孔に対する、前記貫通孔Aの割合が30%以上である請求項1~5のいずれか1項に記載のアルミニウム板。
- 前記アルミニウム板の厚さが、5μm~100μmである請求項1~6のいずれか1項に記載のアルミニウム板。
- 前記アルミニウム板の主面に平均開口径が0.1μm~100μmの貫通していない凹部を有する請求項1~7のいずれか1項に記載のアルミニウム板。
- 前記凹部の密度が、1000~500000個/mm2である請求項8に記載のアルミニウム板。
- 前記凹部間の最短ピッチが0.01μm~10μmである請求項8または9に記載のアルミニウム板。
- アルミニウム基材の表面に水酸化アルミニウムを主成分とする水酸化アルミニウム皮膜を形成する皮膜形成工程と、
前記皮膜形成工程の後に、貫通孔形成処理を行って貫通孔を形成する貫通孔形成工程と、
前記貫通孔形成工程の後に、前記水酸化アルミニウム皮膜を除去する皮膜除去工程とを有することを特徴とするアルミニウム板の製造方法。 - 前記皮膜形成工程は、硝酸、塩酸、硫酸、燐酸、シュウ酸、あるいは、これらの2以上の混酸を用いて電気化学的処理を行って、前記水酸化アルミニウム皮膜を形成する請求項11に記載のアルミニウム板の製造方法。
- 前記貫通孔形成工程は、硝酸、塩酸、硫酸、燐酸、シュウ酸、あるいは、これらの2以上の混酸を用いて電気化学的溶解処理を行って、前記貫通孔を形成する請求項11または12に記載のアルミニウム板の製造方法。
- 前記皮膜除去工程は、硝酸、塩酸、硫酸、燐酸、シュウ酸、あるいは、これらの2以上の混酸、または、水酸化ナトリウムを用いて化学的溶解処理を行って、前記水酸化アルミニウム皮膜を除去する請求項11~13のいずれか1項に記載のアルミニウム板の製造方法。
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