WO2016158245A1 - アルミニウム板および蓄電デバイス用集電体 - Google Patents
アルミニウム板および蓄電デバイス用集電体 Download PDFInfo
- Publication number
- WO2016158245A1 WO2016158245A1 PCT/JP2016/057177 JP2016057177W WO2016158245A1 WO 2016158245 A1 WO2016158245 A1 WO 2016158245A1 JP 2016057177 W JP2016057177 W JP 2016057177W WO 2016158245 A1 WO2016158245 A1 WO 2016158245A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aluminum plate
- aluminum
- holes
- average
- ratio
- Prior art date
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 215
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 238000003860 storage Methods 0.000 title claims abstract description 30
- 230000005611 electricity Effects 0.000 claims description 32
- 238000000034 method Methods 0.000 abstract description 72
- 238000012545 processing Methods 0.000 abstract description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 35
- 238000004519 manufacturing process Methods 0.000 description 33
- 239000000463 material Substances 0.000 description 33
- 239000000758 substrate Substances 0.000 description 29
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 28
- 238000004090 dissolution Methods 0.000 description 28
- 229910017604 nitric acid Inorganic materials 0.000 description 28
- 239000002585 base Substances 0.000 description 27
- 239000008151 electrolyte solution Substances 0.000 description 22
- 239000010410 layer Substances 0.000 description 22
- 238000005868 electrolysis reaction Methods 0.000 description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 18
- 239000011149 active material Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 238000005259 measurement Methods 0.000 description 17
- 238000007788 roughening Methods 0.000 description 17
- -1 nitrate compound Chemical class 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 229910000838 Al alloy Inorganic materials 0.000 description 7
- 239000012670 alkaline solution Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 230000037303 wrinkles Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 239000003990 capacitor Substances 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001553 barium compounds Chemical class 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 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
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 230000005856 abnormality Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 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
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 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
- 230000014759 maintenance of location Effects 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
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 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
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 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
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 239000003463 adsorbent 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 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
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000005097 cold rolling Methods 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940111685 dibasic potassium phosphate Drugs 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- 238000009792 diffusion process Methods 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 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
- 230000000873 masking effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 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
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 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
- 238000011084 recovery Methods 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 238000002407 reforming Methods 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
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 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
- 229910000029 sodium carbonate 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
- 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
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 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
- 239000000126 substance Substances 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
- 230000003746 surface roughness Effects 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
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- 238000007740 vapor deposition Methods 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
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
- B22D11/049—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds for direct chill casting, e.g. electromagnetic casting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on 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
- 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
-
- 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
- C25F3/04—Etching of light metals
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to an aluminum plate and a current collector for an electricity storage device.
- 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.
- Patent Document 1 discloses an aluminum penetrating foil composed of “Fe: 5 to 80 ppm by weight, Si: 5 to 100 ppm by weight, Cu: 10 to 100 ppm by weight, and the balance: Al and inevitable impurities, (1 )
- the foil thickness is 50 ⁇ m or less, (2) a plurality of through-holes from the foil surface to the back surface, and (3) the ratio of the vertical through-hole occupancy c (%) to the foil thickness t ( ⁇ m) in the aluminum through foil [C / t] is 1.4 or more.
- the through hole has an inner diameter of 0.2 to 5 ⁇ m. ([Claim 3]), and further describes that an active material is applied to the aluminum penetration foil ([0036]).
- the present inventors examined a conventionally known aluminum plate described in Patent Document 1 and the like, and depending on the alloy composition of aluminum, breakage, wrinkles, breakage, etc. during production may occur and the process suitability may be inferior. In addition, it has been clarified that the processing characteristics of the aluminum plate to be manufactured may be inferior depending on the size and the opening ratio of the through hole.
- an object of the present invention is to provide an aluminum plate excellent in both process suitability and processing characteristics and a current collector for an electricity storage device using the aluminum plate.
- the shape of the aluminum plate is rectangular or square, Any one of [1] to [3], in which at least one pair of two opposing sides has an average aperture ratio of 0 to 5% at the edge portions of the two opposing sides.
- the edge portion refers to a region having a distance of 50 mm from the end of the aluminum plate constituting the side.
- the shape of the aluminum plate is long, The aluminum plate according to any one of [1] to [3], wherein an average aperture ratio due to the through holes is 2 to 5% at the edge portions of two sides facing each other in the width direction.
- the edge portion refers to a region having a distance of 50 mm from the end of the aluminum plate constituting the side.
- the shape of the aluminum plate is a roll, The aluminum plate according to any one of [1] to [3], wherein an average aperture ratio due to the through holes is 0 to 5% at the edge portions of the two sides facing the roll in the axial direction.
- the edge portion refers to a region having a distance of 50 mm from the end of the aluminum plate constituting the side.
- a current collector for an electricity storage device comprising an aluminum plate having a plurality of through holes in the thickness direction, A current collector for an electricity storage device, wherein the aluminum plate is the aluminum plate according to any one of [1] to [6].
- FIG. 1A is a schematic top view showing an example of the aluminum plate of the present invention.
- 1B is a cross-sectional view taken along line BB in FIG. 1A.
- FIG. 2A is a schematic top view showing an example (rectangular shape) of the embodiment of the aluminum plate of the present invention.
- FIG. 2B is a schematic perspective view showing another example (roll shape) of the embodiment of the aluminum plate of the present invention.
- FIG. 3A is a schematic cross-sectional view of an aluminum base material in a schematic cross-sectional view for explaining an example of a preferable method for producing an aluminum plate of the present invention.
- FIG. 3B is a schematic cross-sectional view for explaining an example of a preferred method for producing an aluminum plate of the present invention, in which a film formation treatment is performed on an aluminum base material and an aluminum hydroxide film is formed on the surface. It is a typical sectional view shown.
- FIG. 3C is a schematic cross-sectional view for explaining an example of a preferred method for producing an aluminum plate of the present invention, in which an electrochemical dissolution treatment is performed after the film formation treatment, and an aluminum substrate and an aluminum hydroxide film It is typical sectional drawing which shows the state in which the through-hole was formed in.
- FIG. 3C is a schematic cross-sectional view for explaining an example of a preferred method for producing an aluminum plate of the present invention, in which an electrochemical dissolution treatment is performed after the film formation treatment, and an aluminum substrate and an aluminum hydroxide film It is typical sectional drawing which shows the state in which the through-hole was formed in.
- FIG. 3D is a schematic cross-sectional view for explaining an example of a preferred method for producing the aluminum plate of the present invention, schematically showing a state after the aluminum hydroxide film is removed after the electrochemical dissolution treatment.
- FIG. 3E is a schematic cross-sectional view for explaining an example of a preferred method for producing the aluminum plate of the present invention, after the aluminum hydroxide film is removed and further subjected to an electrochemical roughening treatment. It is a typical sectional view showing the state.
- FIG. 4A is a schematic cross-sectional view of an aluminum base material in a schematic cross-sectional view for explaining another example of a preferable method for producing an aluminum plate of the present invention.
- FIG. 4B is a schematic cross-sectional view for explaining another example of a preferable method for producing an aluminum plate of the present invention, in which a film formation treatment is performed on an aluminum base, and an aluminum hydroxide film is applied to the front and back surfaces. It is typical sectional drawing which shows the formed state.
- FIG. 4C is a schematic cross-sectional view for explaining another example of the preferred method for producing an aluminum plate of the present invention, in which an electrochemical dissolution treatment is performed after the film formation treatment, and the aluminum substrate and the hydroxylation are treated. It is typical sectional drawing which shows the state which formed the through-hole in the aluminum membrane
- FIG. 4D shows a state after the aluminum hydroxide film is removed after the electrochemical dissolution treatment in a schematic cross-sectional view for explaining another example of the preferred method for producing the aluminum plate of the present invention. It is typical sectional drawing.
- FIG. 4E is a schematic cross-sectional view for explaining another example of the preferred method for producing the aluminum plate of the present invention, and after the aluminum hydroxide film is removed, an electrochemical roughening treatment is further performed. It is typical sectional drawing which shows the state after having performed.
- 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 in the thickness direction, having a thickness of 40 ⁇ m or less, an average opening diameter of the through holes of 0.1 to 100 ⁇ m, and an average opening ratio due to the through holes 2 to 30%, the Fe content is 0.03% by mass or more, and the ratio of the Fe content to the Si content (hereinafter also referred to as “content ratio (Fe / Si)”). ) Is 1.0 or more.
- the thickness of the aluminum plate refers to an average value of thicknesses measured at any five points using a contact-type film thickness meter (digital electronic micrometer).
- the average opening diameter of the through-holes was obtained by photographing the surface of the aluminum plate at a magnification of 100 to 10,000 times from directly above using a high-resolution scanning electron microscope (SEM). Then, at least 20 through-holes whose circumferences are connected in a ring shape are extracted, the diameters are read to obtain the opening diameter, and the average value of these is calculated as the average opening diameter.
- the magnification of the range mentioned above can be selected suitably so that the SEM photograph which can extract 20 or more through-holes is obtained.
- the opening diameter measured the maximum value of the distance between the edge parts of a through-hole part.
- 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 average aperture ratio due to the through hole is determined by installing a parallel light optical unit on one surface side of the aluminum plate, transmitting the parallel light, and using an optical microscope from the other surface of the aluminum substrate. The surface of is taken at a magnification of 100 to obtain a photograph. For the 100 mm ⁇ 75 mm field of view (5 locations) in the 10 cm ⁇ 10 cm range of the obtained photograph, the ratio (opening area / geometrical area) was calculated from the total opening area of the through holes and the field area (geometric area). Area) and the average value in each field of view (5 locations) is calculated as the average aperture ratio.
- the average opening diameter and average opening ratio of the through-holes, and the Fe content and content ratio (Fe / Si) are within the above-described range, so that the process suitability and the thickness are 40 ⁇ m or less. All the processing characteristics are good.
- the present inventors presume as follows. That is, when the Fe content and the content ratio (Fe / Si) are within the above-described ranges, it is considered that both the breaking strength and breaking elongation of the aluminum plate are improved and the process suitability is improved. This can also be inferred from the results shown in Comparative Examples 1 and 2.
- the aluminum plate 10 shown to FIG. 2A is rectangular shape, and the average opening ratio by a through-hole in the edge part 3a of at least 1 set of 2 sides which opposes among 2 sets of 2 sides which opposes in the width direction. Shows an example of 0%.
- the aluminum plate 10 shown in FIG. 2A is rectangular shape, and the average opening ratio by a through-hole in the edge part 3a of at least 1 set of 2 sides which opposes among 2 sets of 2 sides which opposes in the width direction. Shows an example of 0%.
- 2B is in the form of a roll, and is formed by a through hole in the edge portion 3a of two sides facing the axial direction of the roll (the width direction of the long aluminum plate constituting the roll).
- An example in which the average aperture ratio is 0% is shown.
- Base material (aluminum alloy) Especially as a base material (aluminum alloy) of the aluminum plate of this invention, if content of Fe is 0.03 mass% or more and content ratio (Fe / Si) is 1.0 or more, it is especially an aluminum alloy It is not limited, For example, well-known aluminum alloys, such as 3000 series (for example, 3003 material), 8000 series (for example, 8021 material), etc. can be used. As such an aluminum alloy, for example, an aluminum alloy having an alloy number shown in Table 1 below can be used.
- the Fe content is preferably 0.03 to 3.00 mass%, more preferably 0.03 to 2.0 mass%.
- the content ratio (Fe / Si) is preferably 1.0 to 100.0, and more preferably 2.0 to 50.0. From the viewpoint of elongation, it is preferable to heat soften the aluminum substrate during rolling or after completion of rolling.
- the through holes of the aluminum plate of the present invention have an average opening diameter of 0.1 to 100 ⁇ m and an average opening ratio of 2 to 30% due to the through holes.
- the average opening diameter of the through holes is preferably 5 to 50 ⁇ m for the reason that the adhesion to the active material layer is good when the aluminum plate of the present invention is used as a current collector. More preferably, it is 30 ⁇ m.
- the average aperture ratio due to the through holes is 2 to 30% because the pre-doping property of lithium is improved when the aluminum plate of the present invention is used as a current collector, and good handling properties are obtained. Preferably, it is 4 to 20%.
- the process suitability is better, and therefore, at least one set of the two opposite sides of the two sides of the opposite sides.
- the average aperture ratio due to the through holes is preferably 0 to 5%. It is assumed that the average aperture ratio at the edge portion is not more than a specific value of the entire average aperture ratio (2 to 30%) including the edge portion.
- the “edge” refers to a region having a distance (width) from the end of the aluminum plate constituting the side of 50 mm.
- the average aperture ratio is 0%” means that there are no through holes in the edge portion. Note that, as described above, the aluminum plate 10 shown in FIG.
- the average aperture ratio due to the through holes in at least one pair of the two opposite edge portions 3a is 0%. Further, the edge portion where the average opening ratio by the through-hole is 0 to 5% is opposed to the direction (width direction) perpendicular to the conveying direction in the aluminum plate manufacturing process, out of the two sets of two sides facing each other. It is preferable to provide at the two edge portions.
- the average aperture ratio due to the through-holes at the two side edges facing in the width direction is 0 because the process suitability is better. It is preferably ⁇ 5%.
- the average due to the through-holes at the two edge portions facing the axial direction of the roll is preferably 0 to 5%.
- the ratio of through holes having an opening diameter of 5 ⁇ m or less among the through holes is 50% because of good adhesion to the active material layer. It is preferable that:
- the ratio of the through-holes having an opening diameter of 5 ⁇ m or less is 30 mm in the range of 10 cm ⁇ 10 cm of the obtained SEM photograph by taking an SEM photograph in the same manner as the measurement of the average opening diameter of the above-mentioned through-holes.
- the opening diameters of all through holes are measured at 5 fields of view of 30 mm, and the ratio is calculated as the ratio of the number of through holes having an opening diameter of 5 ⁇ m or less to the number of all measured through holes.
- the ratio of the through holes having an opening diameter of more than 30 ⁇ m is 1% or more because of good adhesion to the active material layer. In addition, it is more preferably 20% or more because the coating property when forming the active material layer as well as the adhesion is good.
- the “ratio of through-holes having an opening diameter of more than 30 ⁇ m” is a range of 10 cm ⁇ 10 cm of the obtained SEM photograph by taking an SEM photograph by the same method as the measurement of the average opening diameter of the above-mentioned through-holes. , The diameters of all the through holes are measured at 5 fields of view of 30 mm ⁇ 30 mm, and the ratio is calculated as the ratio of the number of through holes having an opening diameter of more than 30 ⁇ m to the number of all measured through holes.
- the thickness of the aluminum plate of the present invention is 40 ⁇ m or less as described above.
- the aluminum plate preferably has a thickness of 6 to 40 ⁇ m, more preferably 8 to 30 ⁇ m, from the viewpoint of handling properties, conductivity, and mounting thickness when the aluminum plate of the present invention is used as a current collector. Is more preferable.
- the tensile strength, breaking elongation, and yield strength of the aluminum plate are preferably the values shown below.
- the tensile strength, elongation at break and proof stress are values measured by the method described in “Metal Material Tensile Test Method” standardized by JIS Z 2241: 2011. Note that the shape of the test piece used for these measurements is a No. 5 test piece (JISZ2241: 2011), the tensile speed is 2 mm / min, and the testing machine is AGS-H (5KN) manufactured by Shimadzu. Further, the proof stress is a 0.2% plastic deformation stress measured by the offset method.
- the aluminum plate of the present invention preferably has a tensile strength of 15 to 350 N / mm 2 , and more preferably 30 to 270 N / mm 2 .
- the strength per unit width is preferably 3 to 30 N / cm, and more preferably 6 to 20 N / cm.
- the aluminum plate of the present invention preferably has a breaking elongation of 0.3% or more, more preferably 0.3 to 3.0%.
- the aluminum plate of the present invention preferably has a yield strength of 5 N / mm 2 or more, more preferably 10 to 150 N / mm 2 . In the present invention, if the thickness of the aluminum plate of the present invention is 6 to 40 ⁇ m, the above-described values of tensile strength, elongation at break and proof stress (the widest numerical range described above) can be satisfied.
- the contact area with the active material layer and the undercoat is increased, the adhesion is better, and an electrical storage device with excellent device characteristics such as output characteristics, cycle characteristics, and rate characteristics can be produced. Therefore, it is preferable that at least one surface of the aluminum plate has non-penetrating recesses with an average opening diameter of 0.1 ⁇ m to 100 ⁇ m at a ratio of the occupation ratio of 0.5% or more.
- this recessed part can be formed by giving arbitrary roughening processes.
- the average opening diameter of the recesses was measured using a high-resolution scanning electron microscope (SEM), and the surface of the aluminum substrate was photographed at a magnification of 200 to 10,000 times from directly above.
- the opening diameter measured the maximum value of the distance between the edge parts of the opening part of a recessed part. That is, since the shape of the opening 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 recess is used as the opening diameter.
- the occupancy rate of the recesses is the sum of the opening areas of the recesses having the above-described opening diameters for five fields of view of 100 mm ⁇ 75 mm in the range of 10 cm ⁇ 10 cm of the obtained photograph as in the average opening diameter of the recesses. Calculated from the ratio [opening area of the recess / (geometric area ⁇ opening area of the through-hole)] The average value in the visual field (5 locations) is calculated as the occupation ratio.
- the average opening diameter of the recesses is preferably 0.2 ⁇ m to 20 ⁇ m.
- the occupation ratio of the recesses is preferably 30 to 100%.
- the density of the recesses is preferably 2 pieces / mm 2 to 1 ⁇ 10 8 pieces / mm 2 , and preferably 2 pieces / mm 2 to 1 ⁇ 10 6 pieces / mm 2 .
- the density of the recesses was determined by measuring the number of through-holes at 5 fields of view of 100 mm ⁇ 75 mm in the range of 10 cm ⁇ 10 cm of the obtained photograph as in the case of the average opening diameter of the recesses. In terms of the number per mm 2 ), the average value of the values in each field of view (5 locations) is calculated as the density of the recesses.
- the arithmetic average roughness Ra of the surface of the aluminum plate is preferably 0.2 ⁇ m or more, and more preferably 0.2 to 1.5 ⁇ m. Since the arithmetic average roughness Ra is 0.2 ⁇ m or more, the adhesiveness with the active material layer is further improved, and the contact area is increased by increasing the surface area. Therefore, the aluminum plate ( The capacity retention rate and output characteristics of an electricity storage device (in particular, a lithium ion secondary battery, a lithium ion capacitor, etc.) using the current collector are increased.
- an electricity storage device in particular, a lithium ion secondary battery, a lithium ion capacitor, etc.
- the arithmetic average roughness Ra is determined using a contact type (stylus type) surface roughness meter (for example, Surfcom 480A manufactured by Tokyo Seimitsu Co., Ltd.), a stylus ⁇ 2 ⁇ mR, a cutoff wavelength of 0.8 mm, It means the average value of arithmetic average roughness measured at five locations at a measurement speed of 0.3 mm / S and a measurement length of 3 mm (ISO'97 standard) and measured from each location.
- a contact type surface roughness meter
- Surfcom 480A manufactured by Tokyo Seimitsu Co., Ltd.
- stylus ⁇ 2 ⁇ mR for example, Surfcom 480A manufactured by Tokyo Seimitsu Co., Ltd.
- a cutoff wavelength of 0.8 mm It means the average value of arithmetic average roughness measured at five locations at a measurement speed of 0.3 mm / S and a measurement length of 3 mm (ISO'97 standard) and measured from each
- the specific surface area ⁇ S of the surface of the aluminum plate is preferably 2% or more, more preferably 5 to 80%.
- the specific surface area ⁇ S is 2% or more, the contact area with the active material layer or the undercoat is increased, the adhesion is improved, and an electricity storage device with excellent output characteristics, cycle characteristics, rate characteristics, and the like is manufactured. be able to.
- the surface shape is measured by an atomic force microscope (AFM) to obtain three-dimensional data.
- the measurement can be performed, for example, under the following conditions.
- the aluminum plate is cut to a size of 1 cm square, set on a horizontal sample stage on a piezo scanner, the cantilever is approached to the sample surface, and when it reaches the region where the atomic force works, it scans in the XY direction.
- the surface shape (wave structure) of the sample is captured by the displacement of the piezoelectric element in the Z direction.
- a piezo scanner that can scan 150 ⁇ m in the XY direction and 10 ⁇ m in the Z direction is used.
- a cantilever having a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m (SI-DF20, manufactured by NANOPROBE) is used for measurement in the DFM mode (Dynamic Force Mode). Further, the reference plane is obtained by correcting the slight inclination of the sample by approximating the obtained three-dimensional data by least squares. At the time of measurement, the surface of 25 ⁇ m ⁇ 25 ⁇ m is measured at 512 ⁇ 128 points.
- the resolution in the XY direction is 1.9 ⁇ m
- the resolution in the Z direction is 1 nm
- the scan speed is 60 ⁇ m / sec.
- the method for producing an aluminum plate is a method for producing an aluminum plate having a plurality of through-holes penetrating in the thickness direction, and a film forming step of forming a film mainly composed of aluminum hydroxide on the surface of an aluminum substrate;
- a method for producing an aluminum plate comprising: a through-hole forming process for forming a through-hole by performing a through-hole forming process after the film forming process; and a film removing process for removing the aluminum hydroxide film after the through-hole forming process It is.
- each step of the aluminum plate manufacturing method will be described with reference to FIGS. 3A to 3E and FIGS. 4A to 4E, followed by a detailed description of each step.
- FIGS. 3A to 3E and FIGS. 4A to 4E are schematic cross-sectional views showing an example of a preferred embodiment of a method for producing an aluminum plate.
- the aluminum plate is manufactured by forming a film on one main surface of aluminum substrate 1 (both main surfaces in the embodiment shown in FIG. 4).
- a film forming step (FIGS. 3A and 3B, FIG. 4A and FIG. 4B) for forming an aluminum hydroxide film 2 after the treatment, and electrolytic dissolution treatment is performed after the film forming step to form the through hole 5;
- a through hole forming step (FIGS. 3B and 3C, FIG. 4B and FIG.
- FIG. 4C for producing an aluminum plate having an aluminum base material 3 having aluminum and an aluminum hydroxide film 4 having a through hole; Film removal step (FIG. 3C, FIG. 3D, FIG. 4C) for removing aluminum hydroxide film 4 having holes and producing aluminum plate 10 made of aluminum substrate 3 having through holes.
- a and Figure 4D a production method having.
- 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 preferably has a process (FIGS. 3D and 3E, FIGS. 4D and 4E).
- 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, 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. 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, at 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. Of these, nitric acid is preferably used as the acid.
- 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.
- the concave portion can be formed densely by performing a roughening treatment.
- it was set as 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 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.
- 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 is coated 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 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 value in the range of about 0.1 to 20 ⁇ m. It is preferable to perform a boehmite treatment.
- the boehmite treatment uses a reaction in which aluminum reacts with high-temperature water or superheated steam to form a pseudo-boehmite hydrated oxide film.
- water at 100 to 400 ° C. for example, pure water
- Water, deionized water can be adjusted to pH 7-12 and a hydrated oxide film can be formed by immersing the aluminum substrate.
- 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.
- the current collector for an electricity storage device of the present invention (hereinafter also abbreviated as “the current collector of the present invention”) is a current collector for an electricity storage device composed of the above-described aluminum plate of the present invention.
- the aluminum plate has a plurality of through holes in the thickness direction, so that, for example, when used in a lithium ion capacitor, lithium can be pre-doped in a short time. It becomes possible to disperse more uniformly.
- an electrical storage device having excellent adhesion to an active material layer and activated carbon and excellent productivity such as cycle characteristics, output characteristics, and coating suitability can be manufactured.
- the current collector of the present invention when the average opening diameter of the through holes of the aluminum plate is 8 to 30 ⁇ m, the lithium pre-doping performance is improved and the adhesion with the active material layer is improved, An electricity storage device with improved cycle characteristics can be manufactured.
- the surface of the current collector of the present invention is measured by Fourier transform infrared spectroscopy, a peak may be observed at 930 to 962 cm ⁇ 1 , which is due to W. Vedder et al .: Trans. Faraday. Soc., Vol.65 (1969) Considering p561, it is considered that this peak is due to an oxide film formed in air.
- the measurement by Fourier transform infrared spectroscopy is performed under the following conditions.
- the incident angle is set to 75 °, and only parallel polarized light is monitored by a reflection method using a polarizer.
- the resolution is 2 to 4 cm ⁇ 1 and the number of integrations is 1000 times.
- a gold vapor deposition mirror is used for the background, and the peak position is recorded from the measurement result.
- the power storage device of the present invention is a power storage device having a positive electrode, a negative electrode, and an electrolyte solution (electrolyte), and is a power storage device using the current collector of the present invention for at least one of the positive electrode and the negative electrode.
- electrolyte solution electrolyte
- the oxide film that can be generated on the surface of the current collector due to storage and transportation environment of the electricity storage device from the viewpoint of suppressing the generation of the oxide film itself or making the film thickness of the generated oxide film as thin as possible. It is preferable to store in a low humidity environment. Specifically, it is preferable to store in an environment where the relative humidity at a temperature of 25 ° C. is 0 to 20%. Examples of a method for forming such a low-humidity environment include, for example, a method of enclosing a dehumidifying agent such as silica gel when packing an electricity storage device or a current collector; For example, there is a method of making a substantially vacuum state).
- the thickness of the oxide film generated when stored at 25 ° C. and a relative humidity of 8% is about 4 nm
- the thickness of the oxide film generated when stored at 25 ° C. and a relative humidity of 70% is 7.2 nm. .
- the positive electrode using the current collector of the present invention comprises a positive electrode current collector using the current collector of the present invention as a positive electrode, and a layer containing a positive electrode active material formed on the surface of the positive electrode current collector (positive electrode active material layer) ).
- the positive electrode active material and the conductive material, binder, solvent and the like that may be contained in the positive electrode active material layer are described in paragraphs [0077] to [0088] of JP2012-216513A. The described materials can be employed as appropriate, the contents of which are incorporated herein by reference.
- the negative electrode using the current collector of the present invention is a negative electrode having a negative electrode current collector using the current collector of the present invention as a negative electrode and a layer containing a negative electrode active material formed on the surface of the negative electrode current collector. is there.
- the negative electrode active material materials described in paragraph [0089] of Japanese Patent Application Laid-Open No. 2012-216513 can be appropriately employed, and the contents thereof are incorporated herein by reference.
- Example 1 ⁇ Preparation of current collector aluminum substrate> The following treatment was performed on the surface of a roll-shaped aluminum base material having an average thickness of 20 ⁇ m, a width of 300 mm, and a length of 1000 m to prepare an aluminum plate.
- a desired trace component is added to a 99.99% molten aluminum material, the concentration of each trace component is adjusted, and then a slab having a thickness of 500 mm is formed by DC (Direct Hill) casting. Was cast.
- both sides of the obtained slab were chamfered by 20 mm, followed by heat treatment at 500 to 600 ° C. Subsequently, it hot-rolled and rolled thickness to 3 mm.
- the aluminum base material was produced by performing cold rolling.
- 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. As shown in Table 2 below, the current density was 50 A / dm 2 and the amount of electricity was 1000 C / dm 2 or more. 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. As shown in Table 2 below, the current density was 25 A / dm 2 and the amount of electricity was 1000 C / dm 2 or more. After formation of the through hole, it was washed with water by spraying and dried.
- Examples 2 to 14 and Comparative Examples 1 to 5 It is produced by changing the Fe content and content ratio (Fe / Si) in the aluminum base material, or the current density or electric quantity in the aluminum hydroxide film forming treatment or electrolytic dissolution treatment to the values shown in Table 2 below.
- An aluminum plate was produced in the same manner as in Example 1, except that the thickness of the aluminum plate, the average opening diameter of the through holes, the average opening ratio, and the like were changed to the values shown in Table 2 below.
- the Fe content and content ratio (Fe / Si) in the produced aluminum plate are the same values as the Fe content and content ratio (Fe / Si) of the aluminum base material used for production, I omit it from the table.
- Examples 15 to 20 In the electrolytic dissolution treatment (b1), in the edge portions (regions where the distance from the end portion is 50 mm) of two sides facing the direction (width direction) perpendicular to the conveyance direction (rolling direction) of the aluminum base material An aluminum plate was produced in the same manner as in Example 1 except that masking was performed with an insulating material sheet material so that the average aperture ratio of the through holes was a value shown in Table 2 below.
- Example 21 to 24 Aluminum plate produced by changing the Fe content and content ratio (Fe / Si) in an aluminum substrate or the amount of electricity in an aluminum hydroxide film forming treatment or electrolytic dissolution treatment to the values shown in Table 2 below An aluminum plate was produced in the same manner as in Example 1 except that the average opening diameter and average opening ratio of the through holes were changed to the values shown in Table 2 below.
- the Fe content and content ratio (Fe / Si) in the produced aluminum plate are the same values as the Fe content and content ratio (Fe / Si) of the aluminum base material used for production, I omit it from the table.
- Table 2 shows the Fe content and content ratio (Fe / Si) of each aluminum substrate used in Examples 1 to 24 and Comparative Examples 1 to 5.
- Table 2 below shows the conditions of the current density and the amount of electricity in the aluminum hydroxide film forming process (film forming process) and the electrolytic dissolution process (through-hole forming process) applied to each aluminum substrate. Further, the thicknesses of the aluminum plates produced in Examples 1 to 24 and Comparative Examples 1 to 5, the average opening diameter of the through holes, the average opening ratio by the through holes and the average opening ratio at the edge, the average opening diameter of the recesses, and The values measured by the methods described above for the occupation ratio, tensile strength (strength per unit width), and elongation at break are shown in Table 2 below.
- the produced aluminum plate it cut into strip shape so that the conveyance direction (rolling direction) of an aluminum base material might be 300 mm, and the direction orthogonal to a conveyance direction might be 10 mm.
- Eight cut aluminum plates are stacked, wound at an inner diameter of about ⁇ 18 mm, the wound sample is pressed at a weight of 5 kg for 1 minute, and further pressed for 30 seconds and then swelled on a surface plate. Measured. The height after pressing was evaluated as “A” having a height of 6 mm or less, and the height exceeding 6 mm was evaluated as “B”.
- an active material 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 carboxymethyl cellulose are added to water and dispersed. Thus, a slurry was prepared. Next, the prepared slurry is applied to both surfaces of the aluminum plate on which the through holes are formed by a die coater so as to have a total thickness of 200 ⁇ m, dried at 120 ° C. for 30 minutes, and the active material is applied to the surface of the aluminum plate. A layer was formed. The adhesion between the active material layer and the aluminum plate was measured by a peel test method.
- the aluminum plate on which the active material layer produced by the above applicability evaluation was formed was cut into a width of 20 mm to produce an evaluation sample.
- a double-sided tape (3M double-sided tape) was applied to one side of the SUS plate, and an evaluation sample was attached to one side of the double-sided tape.
- a SUS plate portion was fixed to one clamp of a tensile strength tester, and the tip of an evaluation sample bent at 180 degrees was fixed to the other clamp, and a 180-degree peel test was performed.
- the tensile speed was 100 mm / min.
- the tape surface after peeling and the aluminum plate surface for current collector were visually evaluated.
- an area ratio of 99% or more occupied by the active material layer remaining on the current collector aluminum plate surface was evaluated as AA, and the active material layer remaining on the current collector aluminum plate surface occupied
- the area ratio of 95% or more and less than 99% was evaluated as A, and the area ratio occupied by the active material layer remaining on the aluminum plate surface for the current collector was evaluated as B when the area ratio was 90% or more and less than 95%.
- Comparative Example 1 in which the Fe content is less than 0.03% by mass and Comparative Example 2 in which the content ratio (Fe / Si) is less than 1.0 both have tensile properties. It was found that the process suitability was not satisfied. Similarly, it was found that Comparative Example 3 with an average opening diameter larger than 100 ⁇ m and Comparative Example 4 with an average opening ratio larger than 30% are inferior in tensile properties and do not satisfy process suitability. Moreover, it turned out that the comparative example 5 whose average opening diameter is less than 1 micrometer and whose average opening rate is less than 2% is inferior to a processing characteristic.
- the average opening diameter of the through holes is 0.1 to 100 ⁇ m, the average opening ratio is 2 to 30%, the Fe content is 0.03% by mass or more, and the content ratio (Fe / Si ) Is 1.0 or more, it was found that process suitability and processing characteristics are good (Examples 1 to 24). In particular, from comparison between Example 1 and Examples 15 to 20, it was found that the process suitability was improved when the average opening ratio of the edge portion was 0 to 5%. Further, in comparison with Example 2 and Example 23, when the occupancy ratio of the non-penetrating recesses having an average opening diameter of 0.1 ⁇ m to 100 ⁇ m is 0.5% or more, the device characteristics are improved. I understood. Further, from comparison between Example 2 and Example 24, it was found that the device characteristics were good when the arithmetic average roughness Ra of the surface was 0.2 ⁇ m or more.
- the aluminum plate of the present invention includes a heat collector, an oil recovery filter, an electrostatic filter, an antibacterial filter, a liquid reforming filter, a water electrolysis filter, an exhaust gas purification filter, a food filtration filter, a marine organism, in addition to a current collector for an electricity storage device.
- Filtration filter dust filter, DNA filter, fine powder classification filter, solid-liquid separation filter, deodorization filter, photocatalyst carrier, hydrogen generating catalyst carrier, enzyme electrode, noble metal absorbent carrier, antibacterial carrier, adsorbent, absorbent, optics Used for filters, far-infrared cut filters, soundproofing / absorbing materials, electromagnetic wave shields, gas diffusion layers / separators for direct fuel cells, oxygen storage container oxygen supply nets, building materials, lighting applications, metallic decorations, etc. be able to.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
すなわち、以下の構成により上記課題を解決することができることを見出した。
厚みが40μm以下であり、
貫通孔の平均開口径が0.1~100μmであり、
貫通孔による平均開口率が2~30%であり、
Feの含有量が0.03質量%以上であり、かつ、Siの含有量に対するFeの含有量の比率が1.0以上である、アルミニウム板。
[2] 少なくとも片方の表面に、平均開口径が0.1μm~100μmの貫通していない凹部を有し、凹部の占有率が0.5%以上である、[1]に記載のアルミニウム板。
[3] 表面の算術平均粗さRaが、0.2μm以上である、[1]または[2]に記載のアルミニウム板。
[4] アルミニウム板の形状が、長方形または正方形であり、
対向する2組の2辺のうち、少なくとも1組の対向する2辺の辺縁部における、貫通孔による平均開口率が0~5%である、[1]~[3]のいずれかに記載のアルミニウム板。
ここで、辺縁部とは、辺を構成するアルミニウム板の端部からの距離が50mmの領域をいう。
[5] アルミニウム板の形状が、長尺状であり、
幅方向に対向する2辺の辺縁部における、貫通孔による平均開口率が0~5%である、[1]~[3]のいずれかに記載のアルミニウム板。
ここで、辺縁部とは、辺を構成するアルミニウム板の端部からの距離が50mmの領域をいう。
[6] アルミニウム板の形状が、ロール状であり、
ロールの軸方向に対向する2辺の辺縁部における、貫通孔による平均開口率が0~5%である、[1]~[3]のいずれかに記載のアルミニウム板。
ここで、辺縁部とは、辺を構成するアルミニウム板の端部からの距離が50mmの領域をいう。
[7] 厚み方向に複数の貫通孔を有するアルミニウム板からなる蓄電デバイス用集電体であって、
アルミニウム板が、[1]~[6]のいずれかに記載のアルミニウム板である、蓄電デバイス用集電体。
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、厚み方向に複数の貫通孔を有するアルミニウム板であって、厚みが40μm以下であり、貫通孔の平均開口径が0.1~100μmであり、貫通孔による平均開口率が2~30%であり、Feの含有量が0.03質量%以上であり、かつ、Siの含有量に対するFeの含有量の比率(以下、「含有比(Fe/Si)」ともいう。)が1.0以上である、アルミニウム板である。
なお、倍率は、貫通孔を20個以上抽出できるSEM写真が得られるように上述した範囲の倍率を適宜選択することができる。また、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。
これは、詳細には明らかではないが、本発明者らは以下のように推測している。
すなわち、Fe含有量および含有比(Fe/Si)が上述した範囲内であることにより、アルミニウム板の破断強度および破断伸びがいずれも向上し、工程適性が良好になったと考えられる。これは、比較例1および2に示す結果からも推察することができる。
また、貫通孔の平均開口径および平均開口率が上述した範囲内であることにより、アルミニウム板の破断強度および破断伸びのバランスが良好となり、加工適性が良好になったと考えられる。これは、比較例3~5に示す結果からも推察することができる。
また、図2Aに示すアルミニウム板10は、長方形状であり、幅方向に対向する2組の2辺のうち、少なくとも1組の対向する2辺の辺縁部3aにおける、貫通孔による平均開口率が0%の例を示す。
同様、図2Bに示すアルミニウム板10は、ロール状であり、ロールの軸方向(ロールを構成する長尺状のアルミニウム板の幅方向)に対向する2辺の辺縁部3aにおける、貫通孔による平均開口率が0%の例を示す。
本発明のアルミニウム板の基材(アルミニウム合金)としては、Feの含有量が0.03質量%以上であり、かつ、含有比(Fe/Si)が1.0以上のアルミニウム合金であれば特に限定されず、例えば、3000系(例えば、3003材など)、8000系(例えば、8021材など)等の公知のアルミニウム合金を用いることができる。
このようなアルミニウム合金としては、例えば、下記第1表に示す合金番号のアルミニウム合金を用いることができる。
また、伸びの観点から、含有比(Fe/Si)は1.0~100.0であるのが好ましく、2.0~50.0であるのがより好ましい。なお、伸びの観点からは、圧延中または圧延終了後に、アルミニウム基材に熱軟化を施すことが好ましい。
本発明のアルミニウム板が有する貫通孔は、上述した通り、貫通孔の平均開口径が0.1~100μmであり、また、貫通孔による平均開口率が2~30%である。
ここで、貫通孔の平均開口径は、本発明のアルミニウム板を集電体として用いた際に活物質層との密着性が良好となる理由から、5~50μmであるのが好ましく、8~30μmであるのがより好ましい。
また、貫通孔による平均開口率は、本発明のアルミニウム板を集電体として用いた際にリチウムのプレドープ性が良くなること、また、良好なハンドリング性が得られるという理由から、2~30%であるのが好ましく、4~20%であるのがより好ましい。
ここで、「辺縁部」とは、辺を構成するアルミニウム板の端部からの距離(幅)が50mmの領域をいう。
また、「平均開口率が0%である」とは、辺縁部に貫通孔を有していないことを表す。なお、上述した通り、図2Aに示すアルミニウム板10は、少なくとも1組の対向する2辺の辺縁部3aにおける貫通孔による平均開口率が0%の例である。
更に、貫通孔による平均開口率が0~5%となる辺縁部は、対向する2組の2辺のうち、アルミニウム板の製造過程における搬送方向と垂直な方向(幅方向)に対向している2辺の辺縁部に設けるのが好ましい。
同様の理由から、アルミニウム板の形状がロール状である場合、ロールの軸方向(ロールを構成する長尺状のアルミニウム板の幅方向)に対向する2辺の辺縁部における、貫通孔による平均開口率が0~5%であるのが好ましい。
ここで、開口径が5μm以下の貫通孔の比率は、上述の貫通孔の平均開口径の測定と同様の方法でSEM写真を撮影し、得られたSEM写真の10cm×10cmの範囲において、30mm×30mmの視野、5箇所で、全ての貫通孔の開口径を測定し、測定した全ての貫通孔の個数に対する、開口径5μm以下の貫通孔の個数の比率として算出する。
ここで、「開口径が30μm超の貫通孔の比率」とは、上述の貫通孔の平均開口径の測定と同様の方法でSEM写真を撮影し、得られたSEM写真の10cm×10cmの範囲において、30mm×30mmの視野、5箇所で、全ての貫通孔の開口径を測定し、測定した全ての貫通孔の個数に対する、開口径30μm超の貫通孔の個数の比率として算出する。
本発明のアルミニウム板の厚みは、上述した通り、40μm以下である。
本発明においては、ハンドリング性、導電性、本発明のアルミニウム板を集電体として用いた際の実装厚みの観点から、アルミニウム板の厚みは6~40μmであるのが好ましく、8~30μmであるのがより好ましい。
本発明においては、ハンドリング性の観点から、アルミニウム板の引張強度、破断伸び、耐力が以下に示す値であるのが好ましい。
ここで、引張強度、破断伸びおよび耐力は、JIS Z 2241:2011で規格される「金属材料引張試験方法」に記載された方法で測定した値をいう。なお、これらの測定に用いる試験片形状は、5号試験片(JISZ2241:2011)を使用し、引張速度は2mm/min、試験機は島津製AGS-H(5KN)を使用する。また、耐力は、オフセット法で測定した0.2%塑性変形する応力とする。
<引張強度>
本発明のアルミニウム板は、引張強度が15~350N/mm2であるのが好ましく、30~270N/mm2であるのがより好ましい。なお、単位幅当たりの強度としては、3~30N/cmであるのが好ましく、6~20N/cmであるのがより好ましい。
<破断伸び>
本発明のアルミニウム板は、破断伸びが0.3%以上であるのが好ましく、0.3~3.0%であるのがより好ましい。
<耐力>
本発明のアルミニウム板は、耐力が5N/mm2以上であるのが好ましく、10~150N/mm2であるのがより好ましい。
なお、本発明においては、本発明のアルミニウム板の厚みが6~40μmであれば、上述した引張強度、破断伸びおよび耐力の各値(上述した最も広い数値範囲)を満たすことが可能となる。
本発明においては、活物質層やアンダーコートとの接触面積が増加して密着性がより良好となり、出力特性、サイクル特性、レート特性等のデバイス特性が良好な蓄電デバイスを作製することができる理由から、アルミニウム板の少なくとも片方の表面に、平均開口径が0.1μm~100μmの貫通していない凹部を占有率が0.5%以上となる割合で有しているのが好ましい。なお、この凹部は、上述した本発明の製造方法において、任意の粗面化処理を施すことにより、形成することができる。
ここで、凹部の平均開口径は、高分解能走査型電子顕微鏡(SEM)を用いてアルミニウム基材の表面を真上から倍率200倍~10000倍で撮影し、得られたSEM写真において、周囲が環状に連なっている凹凸構造の凹部(ピット)を少なくとも20個抽出(ただし、凹部が20個ないものはすべての凹部を抽出)し、その直径を読み取って開口径とし、これらの平均値を平均開口径として算出する。なお、開口径は、凹部の開口部の端部間の距離の最大値を測定した。すなわち、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、凹部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以上の凹部が一体化したような形状の凹部の場合にも、これを1つの凹部とみなし、開口部の端部間の距離の最大値を開口径とする。
また、凹部の占有率は、凹部の平均開口径と同様、得られた写真の10cm×10cmの範囲において、100mm×75mmの視野、5箇所について、上述した開口径を有する凹部の開口面積の合計と視野の面積(幾何学的面積)から貫通孔の開口面積を除いた表面の面積とから、比率〔凹部の開口面積/(幾何学的面積-貫通孔の開口面積)〕から算出し、各視野(5箇所)における平均値を占有率として算出する。
また、凹部の平均開口径は、0.2μm~20μmであるのが好ましい。
同様に、凹部の占有率は、30~100%であるのが好ましい。
ここで、凹部の密度は、凹部の平均開口径と同様、得られた写真の10cm×10cmの範囲において、100mm×75mmの視野、5箇所について、貫通孔の個数を計測し、1平方ミリメートル(mm2)あたりの個数に換算し、各視野(5箇所)における値の平均値を凹部の密度として算出する。
本発明においては、アルミニウム板の表面の算術平均粗さRaが、0.2μm以上であるのが好ましく、0.2~1.5μmであるのがより好ましい。
算術平均粗さRaが0.2μm以上であることにより、活物質層との密着性がより向上するとともに、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(特に、リチウムイオン二次電池、リチウムイオンキャパシタなど)の容量維持率や出力特性が高くなる。
ここで、算術平均粗さRaは、接触式(触針式)の表面粗さ計(例えば、(株)東京精密製のサーフコム 480Aなど)を用い、触針φ2μmR、カットオフ波長0.8mm、測定速度0.3mm/S、測定長3mm(ISO’97規格)にて5箇所測定して、各箇所から測定される算術平均粗さの平均値をいう。
本発明においては、アルミニウム板の表面の比表面積ΔSが2%以上であるのが好ましく、5~80%であるのがより好ましい。
比表面積ΔSが2%以上であることにより、活物質層やアンダーコートとの接触面積が増加して密着性がより良好となり、出力特性、サイクル特性、レート特性等が良好な蓄電デバイスを作製することができる。
ここで、比表面積ΔSは、原子間力顕微鏡を用いて、表面の25μm×25μmの範囲を512×128点測定して得られる3次元データから近似三点法により得られる実面積Sxと、幾何学的測定面積S0とから、下記式(i)により求められる値である。
ΔS=(Sx-S0)/S0×100(%)・・・(i)
すなわち、アルミニウム板を1cm角の大きさに切り取って、ピエゾスキャナー上の水平な試料台にセットし、カンチレバーを試料表面にアプローチし、原子間力が働く領域に達したところで、XY方向にスキャンし、その際、試料の表面形状(波構造)をZ方向のピエゾの変位でとらえる。ピエゾスキャナーは、XY方向について150μm、Z方向について10μm、走査可能なものを使用する。カンチレバーは共振周波数120~150kHz、バネ定数12~20N/mのもの(SI-DF20、NANOPROBE社製)を用い、DFMモード(Dynamic Force Mode)で測定する。また、求めた3次元データを最小二乗近似することにより試料のわずかな傾きを補正し基準面を求める。計測の際は、表面の25μm×25μmの範囲を512×128点測定する。XY方向の分解能は1.9μm、Z方向の分解能は1nm、スキャン速度は60μm/secとする。
上記で求められた3次元データ(f(x,y))を用い、隣り合う3点を抽出し、その3点で形成される微小三角形の面積の総和を求め、実面積Sxとする。表面積差ΔSは、得られた実面積Sxと幾何学的測定面積S0とから、上記式(i)により求められる。
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3A~図3Eおよび図4A~図4Eに示すように、アルミニウム基材1の一方の主面(図4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3Aおよび図3B,図4Aおよび図4B)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3Bおよび図3C,図4Bおよび図4C)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3Cおよび図3D,図4Cおよび図4D)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3Dおよび図3E,図4Dおよび図4E)を有しているのが好ましい。
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℃以上で電解を行ったりすることができる。
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℃以上で電解を行ったりすることができる。
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、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0.1~20μm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。
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0.1~20μm程度の範囲で小さく調整できる理由から、上述した皮膜除去工程の後に、ベーマイト処理を施すのが好ましい。
ここで、ベーマイト処理は、アルミニウムが高温の水や過熱水蒸気と反応して擬ベーマイト質の水和酸化皮膜を生成する反応を用いたものであり、例えば、100~400℃の水(例えば、純水、脱イオン水)をpH7~12に調整し、アルミニウム基材を浸漬することによって水和酸化皮膜を生成することができる。
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。
本発明の蓄電デバイス用集電体(以下、「本発明の集電体」とも略す。)は、上述した本発明のアルミニウム板で構成される蓄電デバイス用の集電体である。
本発明の集電体は、アルミニウム板が厚み方向に複数の貫通孔を有していることにより、例えば、リチウムイオンキャパシタに用いた場合においては短時間でのリチウムのプレドープが可能となり、リチウムをより均一に分散させることが可能となる。また、活物質層や活性炭との密着性が良好となり、サイクル特性や出力特性、塗布適性等の生産性に優れる蓄電デバイスを作製することができる。
特に、本発明の集電体は、アルミニウム板の貫通孔の平均開口径が8~30μmであると、リチウムのプレド-プ性能が向上すると共に、活物質層との密着性がより良好となり、サイクル特性が向上した蓄電デバイスを作製することができる。
また、本発明の集電体の表面をフーリエ変換赤外分光法によって測定すると、930~962cm-1にピークが観測されることがあるが、これは、W. Vedder et al.:Trans. Faraday Soc., Vol.65 (1969) p561を考慮すると、空気中で生成した酸化皮膜に起因するピークであると考えられる。
ここで、フーリエ変換赤外分光法による測定は、以下の条件で行う。まず、入射角75°に設定し、偏光子を用いて平行偏光のみを反射法にてモニタリングする。次いで、分解能を2~4cm-1とし、積算回数は1000回とする。バックグラウンドには金蒸着ミラーを用い、測定結果よりピーク位置を記録する。
本発明の蓄電デバイスは、正極と、負極と、電解液(電解質)とを有する蓄電デバイスであり、正極および負極の少なくとも一方に本発明の集電体を用いた蓄電デバイスである。
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。
また、本発明においては、蓄電デバイスの保管や輸送環境によって集電体表面に生成し得る酸化皮膜に関して、酸化皮膜の生成自体の抑制または生成される酸化皮膜の膜厚をできるだけ薄くする観点から、低湿環境下で保存することが好ましい。具体的には、25℃の温度下での相対湿度が0~20%となる環境下で保存することが好ましい。このような低湿環境の形成方法としては、例えば、蓄電デバイスまたは集電体を梱包する際に、シリカゲルなどの除湿剤を同包する方法;蓄電デバイスまたは集電体をポリエチレンで覆って減圧状態(例えば、略真空状態)にする方法;などが挙げられる。なお、25℃相対湿度8%下で保管した場合に生成する酸化皮膜の厚みは4nm程度であり、25℃相対湿度70%下で保管した場合に生成する酸化皮膜の厚みは7.2nmである。
本発明の集電体を用いた正極は、本発明の集電体を正極に用いた正極集電体と、正極集電体の表面に形成される正極活物質を含む層(正極活物質層)とを有する正極である。
ここで、上記正極活物質や、上記正極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。
本発明の集電体を用いた負極は、本発明の集電体を負極に用いた負極集電体と、負極集電体の表面に形成される負極活物質を含む層とを有する負極である。
ここで、上記負極活物質については、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。
<集電体用アルミニウム基材の作製>
平均厚さ20μm、幅300mm、長さ1000mのロール状のアルミニウム基材の表面に、以下に示す処理を施し、アルミニウム板を作製した。
アルミニウム基材の作製については、最初に、99.99%アルミ材溶湯に所望の微量成分を添加し、各微量成分の濃度調整を行った後に、DC(Direct Chill)鋳造で厚さ500mmのスラブを鋳造した。
次いで、得られたスラブの両面を20mm面削した後、500~600℃で熱処理を施した。
次いで、熱間圧延を施して厚さを3mmまで圧延した。
次いで、冷間圧延を施すことにより、アルミニウム基材を作製した。
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。なお、下記第2表に示す通り、電流密度は、50A/dm2とし、電気量は、1000C/dm2以上とした。
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。なお、下記第2表に示す通り、電流密度は、25A/dm2とし、電気量は、1000C/dm2以上とした。
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、硝酸1%、アルミニウムイオン濃度0.5質量%の水溶液(液温30℃)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。なお、作製されたアルミニウム板の厚みを下記第2表に示す。
アルミニウム基材におけるFe含有量および含有比(Fe/Si)、あるいは、水酸化アルミニウム皮膜形成処理または電解溶解処理における電流密度もしくは電気量を下記第2表に示す値に変更することにより、作製されるアルミニウム板の厚み、貫通孔の平均開口径および平均開口率などが下記第2表に示す値に変更された以外は、実施例1と同様の方法により、アルミニウム板を作製した。
なお、作製されたアルミニウム板におけるFe含有量および含有比(Fe/Si)は、作製に用いたアルミニウム基材のFe含有量および含有比(Fe/Si)と同じ値であるため、下記第2表からは割愛している。
上記電解溶解処理(b1)において、アルミニウム基材の搬送方向(圧延方向)と垂直な方向(幅方向)に対向している2辺の辺縁部(端部からの距離が50mmの領域)における貫通孔の平均開口率が下記第2表に示す値となるように、絶縁材料シート材にてマスキングを施した以外は、実施例1と同様の方法により、アルミニウム板を作製した。
アルミニウム基材におけるFe含有量および含有比(Fe/Si)、あるいは、水酸化アルミニウム皮膜形成処理または電解溶解処理における電気量を下記第2表に示す値に変更することにより、作製されるアルミニウム板の貫通孔の平均開口径および平均開口率などが下記第2表に示す値に変更された以外は、実施例1と同様の方法により、アルミニウム板を作製した。
なお、作製されたアルミニウム板におけるFe含有量および含有比(Fe/Si)は、作製に用いたアルミニウム基材のFe含有量および含有比(Fe/Si)と同じ値であるため、下記第2表からは割愛している。
また、各アルミニウム基材に対して施した水酸化アルミニウム皮膜形成処理(皮膜形成工程)および電解溶解処理(貫通孔形成工程)の電流密度および電気量の条件を下記第2表に示す。
また、実施例1~24および比較例1~5で作製した各アルミニウム板の厚み、貫通孔の平均開口径、貫通孔による平均開口率および辺縁部における平均開口率、凹部の平均開口径および占有率、ならびに、引張強度(単位幅当たりの強度)および破断伸びについて、上述した方法により測定した値を下記第2表に示す。
また、実施例1~24および比較例1~5で作製した各アルミニウム板の表面の算術平均粗さRaを、(株)東京精密製のサーフコム 480Aを用い、以下に示す測定条件(ISO’97規格)で5箇所測定して、各箇所から測定される算術平均粗さの平均値を算出した。測定結果を下記第2表に示す。
<測定条件>
・触針:φ2μmR
・カットオフ波長:0.8mm
・測定速度:0.3mm/S
・測定長:3mm
・総合解析ソフトウェア AccTee使用
作製した各アルミニウム板を用いて、長さ1000mのロール状のサンプルを作製し、送り出し装置、塗布装置、および、巻き取り装置を用いて、5m/minの速度でハンドリング試験を行った。
その結果、破断の発生については、破断の有無を確認し、破断がないものを「A」と評価し、破断があるものを「B」と評価した。
また、シワ・折れの発生については、シワ・折れの有無を確認し、シワ・折れがないものを「AA」と評価し、シワ・折れが僅かに発生するが破断などの工程異常を起こさないものを「B」と評価し、シワ・折れが発生し、破断などの工程異常を起こすものを「C」と評価した。
作製したアルミニウム板について、アルミニウム基材の搬送方向(圧延方向)が300mmとなり、搬送方向に直交する方向が10mmとなるように、短冊状にカットした。
カットしたアルミニウム板を8枚重ね合わせ、内径約φ18mmで捲回し、捲回したサンプルを重さ5Kgで1分間プレスし、更に30秒間プレス後に定盤の上で膨らんだ状態の捲回サンプルの高さを測定した。
プレス後の高さが、6mm以下のもの「A」と評価し、6mmを超えるものを「B」と評価した。
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、スラリーを調製した。
次に、調製したスラリーを、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。
活物質層とアルミニウム板との密着性をピール試験方法により測定した。
具体的には、上記塗布性の評価で作製した活物質層を形成したアルミニウム板を幅20mmに裁断して評価サンプルを作製した。
SUS板の片面に両面テープ(3M社製両面テープ)を貼り付け、両面テープの片面に評価サンプルを貼り付けた。引張強度試験機の一方のクランプにSUS板の部分を固定し、他方のクランプに180度に折り曲げた評価サンプルの先端を固定し、180度剥離試験を行った。引張速度は、100mm/minとした。
剥離後のテープ面と集電体用アルミニウム板面を目視で評価した。
具体的には、集電体用アルミニウム板面に残存した活物質層が占める面積率が99%以上であるものをAAと評価し、集電体用アルミニウム板面に残存した活物質層が占める面積率が95%以上99%未満であるものをAと評価し、集電体用アルミニウム板面に残存した活物質層が占める面積率が90%以上95%未満であるものをBと評価した。
同様に、平均開口径が100μmより大きい比較例3や、平均開口率が30%より大きい比較例4は、いずれも、引張特性が劣り、工程適性を満足しないことが分かった。
また、平均開口径が1μm未満であり、平均開口率が2%未満である比較例5は、加工特性に劣ることが分かった。
一方、貫通孔の平均開口径が0.1~100μmであり、平均開口率が2~30%であり、Feの含有量が0.03質量%以上であり、かつ、含有比(Fe/Si)が1.0以上であると、工程適性および加工特性が良好となることが分かった(実施例1~24)。
特に、実施例1と実施例15~20との対比から、辺縁部の平均開口率が0~5%であると、工程適性がより良好となることが分かった。
また、実施例2と実施例23との対比から、平均開口径が0.1μm~100μmの貫通していない凹部の占有率が0.5%以上であると、デバイス特性が良好となることが分かった。
また、実施例2と実施例24との対比から、表面の算術平均粗さRaが、0.2μm以上であると、デバイス特性が良好となることが分かった。
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
10 アルミニウム板
Claims (7)
- 厚み方向に複数の貫通孔を有するアルミニウム板であって、
厚みが40μm以下であり、
前記貫通孔の平均開口径が0.1~100μmであり、
前記貫通孔による平均開口率が2~30%であり、
Feの含有量が0.03質量%以上であり、かつ、Siの含有量に対するFeの含有量の比率が1.0以上である、アルミニウム板。 - 少なくとも片方の表面に、平均開口径が0.1μm~100μmの貫通していない凹部を有し、前記凹部の占有率が0.5%以上である、請求項1に記載のアルミニウム板。
- 表面の算術平均粗さRaが、0.2μm以上である、請求項1または2に記載のアルミニウム板。
- 前記アルミニウム板の形状が、長方形または正方形であり、
対向する2組の2辺のうち、少なくとも1組の対向する2辺の辺縁部における、前記貫通孔による平均開口率が0~5%である、請求項1~3のいずれか1項に記載のアルミニウム板。
ここで、辺縁部とは、辺を構成するアルミニウム板の端部からの距離が50mmの領域をいう。 - 前記アルミニウム板の形状が、長尺状であり、
幅方向に対向する2辺の辺縁部における、前記貫通孔による平均開口率が0~5%である、請求項1~3のいずれか1項に記載のアルミニウム板。
ここで、辺縁部とは、辺を構成するアルミニウム板の端部からの距離が50mmの領域をいう。 - 前記アルミニウム板の形状が、ロール状であり、
ロールの軸方向に対向する2辺の辺縁部における、前記貫通孔による平均開口率が0~5%である、請求項1~3のいずれか1項に記載のアルミニウム板。
ここで、辺縁部とは、辺を構成するアルミニウム板の端部からの距離が50mmの領域をいう。 - 厚み方向に複数の貫通孔を有するアルミニウム板からなる蓄電デバイス用集電体であって、
前記アルミニウム板が、請求項1~6のいずれか1項に記載のアルミニウム板である、蓄電デバイス用集電体。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16772129.9A EP3279984B1 (en) | 2015-03-31 | 2016-03-08 | Aluminum plate, and current collector for power storage device |
JP2017509461A JP6592506B2 (ja) | 2015-03-31 | 2016-03-08 | アルミニウム板および蓄電デバイス用集電体 |
KR1020177026067A KR20170118806A (ko) | 2015-03-31 | 2016-03-08 | 알루미늄판 및 축전 디바이스용 집전체 |
CN201680015737.8A CN107431209A (zh) | 2015-03-31 | 2016-03-08 | 铝板和蓄电装置用集电体 |
US15/693,551 US20180013148A1 (en) | 2015-03-31 | 2017-09-01 | Aluminum plate and collector for storage device |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015074150 | 2015-03-31 | ||
JP2015-074150 | 2015-03-31 | ||
JP2015-152373 | 2015-07-31 | ||
JP2015152373 | 2015-07-31 | ||
JP2015-236064 | 2015-12-02 | ||
JP2015236064 | 2015-12-02 | ||
JP2016-021786 | 2016-02-08 | ||
JP2016021786 | 2016-02-08 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/693,551 Continuation US20180013148A1 (en) | 2015-03-31 | 2017-09-01 | Aluminum plate and collector for storage device |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016158245A1 true WO2016158245A1 (ja) | 2016-10-06 |
Family
ID=57005706
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/057177 WO2016158245A1 (ja) | 2015-03-31 | 2016-03-08 | アルミニウム板および蓄電デバイス用集電体 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20180013148A1 (ja) |
EP (1) | EP3279984B1 (ja) |
JP (1) | JP6592506B2 (ja) |
KR (1) | KR20170118806A (ja) |
CN (1) | CN107431209A (ja) |
TW (1) | TW201639975A (ja) |
WO (1) | WO2016158245A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109273720A (zh) * | 2017-07-18 | 2019-01-25 | 福田金属箔粉工业株式会社 | 开孔金属箔 |
WO2019077995A1 (ja) * | 2017-10-16 | 2019-04-25 | 富士フイルム株式会社 | アルミニウム箔および電極用アルミニウム部材 |
JP2020194845A (ja) * | 2019-05-27 | 2020-12-03 | 旭化成株式会社 | 正極前駆体 |
US12002965B2 (en) | 2019-08-22 | 2024-06-04 | Fujifilm Corporation | Aluminum foil |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018155468A1 (ja) * | 2017-02-27 | 2018-08-30 | 太陽誘電株式会社 | 電気化学デバイス |
CN110819854B (zh) * | 2019-11-19 | 2021-07-20 | 安徽鑫发铝业有限公司 | 一种空气净化器用抗菌铝型材 |
CN113231469B (zh) * | 2021-05-10 | 2023-04-18 | 贵州大学 | 一种锌基复合材料用铝合金材料包套热轧的方法 |
WO2024055187A1 (zh) * | 2022-09-14 | 2024-03-21 | 宁德时代新能源科技股份有限公司 | 集流体、极片、电极组件、电池单体、电池以及用电装置 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009064770A (ja) * | 2007-08-09 | 2009-03-26 | Panasonic Corp | 非水電解質二次電池及びその製造方法 |
WO2010029675A1 (ja) * | 2008-09-09 | 2010-03-18 | パナソニック株式会社 | 非水電解質二次電池及びその製造方法 |
WO2010100924A1 (ja) * | 2009-03-05 | 2010-09-10 | 東洋アルミニウム株式会社 | 集電体用アルミニウム合金箔およびその製造方法 |
JP2011216364A (ja) * | 2010-03-31 | 2011-10-27 | Toyo Aluminium Kk | 負極集電体用金属箔 |
JP2012021205A (ja) * | 2010-07-16 | 2012-02-02 | Kobe Steel Ltd | 電池集電体用アルミニウム硬質箔 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008078777A1 (ja) * | 2006-12-27 | 2008-07-03 | Jm Energy Corporation | 塗布電極及び有機電解質キャパシタ |
WO2011004777A1 (ja) * | 2009-07-07 | 2011-01-13 | 東洋アルミニウム株式会社 | アルミニウム貫通箔 |
US9331339B2 (en) * | 2009-09-30 | 2016-05-03 | Toyo Aluminium Kabushiki Kaisha | Perforated aluminium foil and manufacturing method thereof |
DK2492994T3 (en) * | 2009-10-23 | 2019-01-28 | Sei Corp | PROCEDURE FOR MANUFACTURING A LITHIUM SECONDARY BATTERY AND APPARATUS |
JP2011249150A (ja) * | 2010-05-27 | 2011-12-08 | Mitsubishi Alum Co Ltd | 蓄電デバイス集電体用アルミニウム箔及び蓄電デバイス集電体 |
WO2013146369A1 (ja) * | 2012-03-29 | 2013-10-03 | 古河スカイ株式会社 | 電極集電体用アルミニウム合金箔およびその製造方法 |
EP2843067A4 (en) * | 2012-04-24 | 2016-04-20 | Uacj Corp | ALUMINUM ALLOY FOIL FOR AN ELECTRODE CURRENT, METHOD FOR THE MANUFACTURE THEREOF AND LITHIUM ION SECONDARY BATTERY |
JP5914439B2 (ja) * | 2013-09-09 | 2016-05-11 | 富士フイルム株式会社 | 二次電池集電体用アルミニウム基材、二次電池集電体用アルミニウム基材の製造方法、二次電池集電体、正極、負極および二次電池 |
-
2016
- 2016-03-08 CN CN201680015737.8A patent/CN107431209A/zh active Pending
- 2016-03-08 EP EP16772129.9A patent/EP3279984B1/en active Active
- 2016-03-08 JP JP2017509461A patent/JP6592506B2/ja active Active
- 2016-03-08 WO PCT/JP2016/057177 patent/WO2016158245A1/ja active Application Filing
- 2016-03-08 KR KR1020177026067A patent/KR20170118806A/ko not_active Application Discontinuation
- 2016-03-14 TW TW105107803A patent/TW201639975A/zh unknown
-
2017
- 2017-09-01 US US15/693,551 patent/US20180013148A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009064770A (ja) * | 2007-08-09 | 2009-03-26 | Panasonic Corp | 非水電解質二次電池及びその製造方法 |
WO2010029675A1 (ja) * | 2008-09-09 | 2010-03-18 | パナソニック株式会社 | 非水電解質二次電池及びその製造方法 |
WO2010100924A1 (ja) * | 2009-03-05 | 2010-09-10 | 東洋アルミニウム株式会社 | 集電体用アルミニウム合金箔およびその製造方法 |
JP2011216364A (ja) * | 2010-03-31 | 2011-10-27 | Toyo Aluminium Kk | 負極集電体用金属箔 |
JP2012021205A (ja) * | 2010-07-16 | 2012-02-02 | Kobe Steel Ltd | 電池集電体用アルミニウム硬質箔 |
Non-Patent Citations (2)
Title |
---|
ALUMINUM HANDBOOK, 31 January 2007 (2007-01-31), pages 19, XP009501308 * |
See also references of EP3279984A4 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109273720A (zh) * | 2017-07-18 | 2019-01-25 | 福田金属箔粉工业株式会社 | 开孔金属箔 |
JP2019021495A (ja) * | 2017-07-18 | 2019-02-07 | 福田金属箔粉工業株式会社 | 開孔金属箔 |
WO2019077995A1 (ja) * | 2017-10-16 | 2019-04-25 | 富士フイルム株式会社 | アルミニウム箔および電極用アルミニウム部材 |
JPWO2019077995A1 (ja) * | 2017-10-16 | 2020-11-05 | 富士フイルム株式会社 | アルミニウム箔および電極用アルミニウム部材 |
US11527758B2 (en) | 2017-10-16 | 2022-12-13 | Fujifilm Corporation | Aluminum foil and aluminum member for electrodes |
JP2020194845A (ja) * | 2019-05-27 | 2020-12-03 | 旭化成株式会社 | 正極前駆体 |
JP7343304B2 (ja) | 2019-05-27 | 2023-09-12 | 旭化成株式会社 | 正極前駆体 |
US12002965B2 (en) | 2019-08-22 | 2024-06-04 | Fujifilm Corporation | Aluminum foil |
Also Published As
Publication number | Publication date |
---|---|
EP3279984A4 (en) | 2018-08-29 |
KR20170118806A (ko) | 2017-10-25 |
TW201639975A (zh) | 2016-11-16 |
CN107431209A (zh) | 2017-12-01 |
EP3279984B1 (en) | 2020-10-21 |
JP6592506B2 (ja) | 2019-10-16 |
EP3279984A1 (en) | 2018-02-07 |
US20180013148A1 (en) | 2018-01-11 |
JPWO2016158245A1 (ja) | 2018-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6592506B2 (ja) | アルミニウム板および蓄電デバイス用集電体 | |
JP6199416B2 (ja) | アルミニウム板の製造方法、アルミニウム板、蓄電デバイス用集電体、蓄電デバイス、防音・吸音材、電磁波シールドおよび建築用材料 | |
JP6374013B2 (ja) | アルミニウム板 | |
WO2016060037A1 (ja) | アルミニウム板およびアルミニウム板の製造方法 | |
WO2017018462A1 (ja) | アルミニウム板およびアルミニウム板の製造方法 | |
WO2016017380A1 (ja) | アルミニウム板 | |
US11527758B2 (en) | Aluminum foil and aluminum member for electrodes | |
CN109791850B (zh) | 电极用铝部件及电极用铝部件的制造方法 | |
WO2022185778A1 (ja) | 集電体用アルミニウム基材、キャパシタ、二次電池、および、集電体用アルミニウム基材の製造方法 | |
JP7190582B2 (ja) | アルミニウム箔 | |
JP6773434B2 (ja) | 金属箔、金属箔の製造方法および蓄電デバイス用集電体 | |
JP7526800B2 (ja) | 集電体用アルミニウム部材、ならびに、リチウムイオンキャパシタ、電気二重層キャパシタ、半固体電池、固体電池、および、非水電解液を使用する二次電池 | |
JP2018035387A (ja) | 孔あき金属基板の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16772129 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017509461 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20177026067 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2016772129 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |