WO2011142338A1 - アルミニウム構造体の製造方法およびアルミニウム構造体 - Google Patents
アルミニウム構造体の製造方法およびアルミニウム構造体 Download PDFInfo
- Publication number
- WO2011142338A1 WO2011142338A1 PCT/JP2011/060722 JP2011060722W WO2011142338A1 WO 2011142338 A1 WO2011142338 A1 WO 2011142338A1 JP 2011060722 W JP2011060722 W JP 2011060722W WO 2011142338 A1 WO2011142338 A1 WO 2011142338A1
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- WO
- WIPO (PCT)
- Prior art keywords
- aluminum
- plating
- layer
- resin molded
- molded body
- Prior art date
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 67
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 477
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 469
- 229920005989 resin Polymers 0.000 claims abstract description 313
- 239000011347 resin Substances 0.000 claims abstract description 309
- 238000007747 plating Methods 0.000 claims abstract description 267
- 150000003839 salts Chemical class 0.000 claims abstract description 219
- 238000000034 method Methods 0.000 claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 claims abstract description 97
- 239000002184 metal Substances 0.000 claims abstract description 97
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 67
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052737 gold Inorganic materials 0.000 claims abstract description 47
- 239000010931 gold Substances 0.000 claims abstract description 47
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 23
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 23
- 239000010948 rhodium Substances 0.000 claims abstract description 23
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 57
- 229910052725 zinc Inorganic materials 0.000 claims description 57
- 239000011701 zinc Substances 0.000 claims description 57
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 52
- 229910000510 noble metal Inorganic materials 0.000 claims description 37
- 238000000465 moulding Methods 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 26
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- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 150000002739 metals Chemical class 0.000 claims description 17
- 238000006467 substitution reaction Methods 0.000 claims description 16
- 238000007772 electroless plating Methods 0.000 claims description 14
- 239000003973 paint Substances 0.000 claims description 13
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 239000012808 vapor phase Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 277
- 239000007772 electrode material Substances 0.000 description 79
- 239000011149 active material Substances 0.000 description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 60
- 239000010408 film Substances 0.000 description 56
- -1 nickel metal hydride Chemical class 0.000 description 34
- 239000011888 foil Substances 0.000 description 32
- 239000006260 foam Substances 0.000 description 31
- 239000011734 sodium Substances 0.000 description 30
- 239000002585 base Substances 0.000 description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 28
- 229910052744 lithium Inorganic materials 0.000 description 28
- 239000007774 positive electrode material Substances 0.000 description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 27
- 229910001416 lithium ion Inorganic materials 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 26
- 239000003990 capacitor Substances 0.000 description 26
- 238000009713 electroplating Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- 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 24
- 239000011230 binding agent Substances 0.000 description 24
- 229910052708 sodium Inorganic materials 0.000 description 24
- 238000005979 thermal decomposition reaction Methods 0.000 description 24
- 239000011261 inert gas Substances 0.000 description 23
- 239000003960 organic solvent Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000002844 melting Methods 0.000 description 20
- 230000008018 melting Effects 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 description 20
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 238000003825 pressing Methods 0.000 description 19
- 239000003792 electrolyte Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 229910000528 Na alloy Inorganic materials 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 16
- 239000012752 auxiliary agent Substances 0.000 description 16
- 239000002482 conductive additive Substances 0.000 description 16
- 238000006073 displacement reaction Methods 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 238000007740 vapor deposition Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000008096 xylene Substances 0.000 description 15
- 238000007599 discharging Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 239000010409 thin film Substances 0.000 description 13
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 12
- 230000005496 eutectics Effects 0.000 description 12
- 238000011049 filling Methods 0.000 description 12
- 150000004693 imidazolium salts Chemical class 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 229920002635 polyurethane Polymers 0.000 description 11
- 239000004814 polyurethane Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- 238000009616 inductively coupled plasma Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 150000004820 halides Chemical class 0.000 description 9
- 239000005486 organic electrolyte Substances 0.000 description 9
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
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- 229910001508 alkali metal halide Inorganic materials 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
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- 239000006229 carbon black Substances 0.000 description 8
- 238000010894 electron beam technology Methods 0.000 description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
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- 239000011777 magnesium Substances 0.000 description 8
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 8
- 238000003466 welding Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000011162 core material Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
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- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 5
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 4
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 4
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 229920006362 Teflon® Polymers 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000008045 alkali metal halides Chemical class 0.000 description 4
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 229910052790 beryllium Inorganic materials 0.000 description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
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- 238000001816 cooling Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 4
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- 230000001678 irradiating effect Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
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- 239000002905 metal composite material Substances 0.000 description 4
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- 229910052700 potassium Inorganic materials 0.000 description 4
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- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
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- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
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- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/08—Perforated or foraminous objects, e.g. sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1137—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers by coating porous removable preforms
-
- 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
- C22C1/08—Alloys with open or closed pores
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0005—Separation of the coating from the substrate
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- 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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- 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
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
- Y10T428/12569—Synthetic resin
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
Definitions
- the present invention relates to a method of forming an aluminum structure on a resin surface by aluminum plating, and particularly to an aluminum structure that can be suitably used as a porous metal body in applications such as various filters and battery electrodes, and a method for producing the same.
- Metal porous bodies having a three-dimensional network structure are used in various fields such as various filters, catalyst carriers, and battery electrodes.
- cermet made of nickel (manufactured by Sumitomo Electric Industries, Ltd .: registered trademark) is used as an electrode material for batteries such as nickel metal hydride batteries and nickel cadmium batteries.
- Celmet is a metal porous body having continuous air holes, and has a feature that the porosity is higher (90% or more) than other porous bodies such as a metal nonwoven fabric. This can be obtained by forming a nickel layer on the surface of the porous resin skeleton having continuous air holes such as urethane foam, then heat-treating it to decompose the foamed resin molded product, and further reducing the nickel.
- the formation of the nickel layer is performed by depositing nickel by electroplating after applying carbon powder or the like to the surface of the skeleton of the foamed resin molded body and conducting a conductive treatment.
- Aluminum has excellent characteristics such as conductivity, corrosion resistance, and light weight.
- a positive electrode of a lithium ion battery in which an active material such as lithium cobaltate is applied to the surface of an aluminum foil is used.
- an active material such as lithium cobaltate
- aluminum is made porous to increase the surface area and the aluminum is filled with an active material. This is because the active material can be used even if the electrode is thickened, and the active material utilization rate per unit area is improved.
- Patent Document 1 discloses that a metal aluminum layer having a thickness of 2 to 20 ⁇ m is formed by subjecting a three-dimensional net-like plastic substrate having an internal communication space to aluminum vapor deposition by an arc ion plating method. A method is described.
- Patent Document 2 a film made of a metal (such as copper) that forms a eutectic alloy below the melting point of aluminum is formed on the skeleton of a foamed resin molding having a three-dimensional network structure, and then an aluminum paste is applied.
- a method is described in which a metal porous body is obtained by performing heat treatment at a temperature of 550 ° C. or higher and 750 ° C. or lower in a non-oxidizing atmosphere to eliminate organic components (foamed resin) and sinter aluminum powder.
- Patent Document 3 uses a low melting point composition in which onium halide and aluminum halide are mixed and melted as a plating bath, and the water content in the bath is 2 wt% or less.
- An aluminum electroplating method is disclosed, in which aluminum is deposited on the cathode while maintaining the same.
- Patent Document 1 an aluminum porous body having a thickness of 2 to 20 ⁇ m is obtained, but since it is based on a gas phase method, it is difficult to produce a large area, and the thickness of the substrate and the pores Depending on the rate, it is difficult to form a uniform layer up to the inside. In addition, there are problems such as a slow formation rate of the aluminum layer and an increase in manufacturing cost due to expensive equipment. According to the method of Patent Document 2, a layer that forms a eutectic alloy with aluminum is formed, and a high-purity aluminum layer cannot be formed.
- the electroplating method of aluminum itself is known, it is only possible to plate on the metal surface, and electroplating on the resin surface, especially on the surface of the porous resin molded body having a three-dimensional network structure.
- the method of electroplating has not been known. This is considered to be affected by problems such as dissolution of the porous resin in the plating bath.
- the present invention provides a method capable of forming an aluminum structure capable of plating aluminum on the surface of a resin molded body, particularly a porous resin molded body having a three-dimensional network structure, and a large
- An object of the present invention is to provide a porous aluminum body that can be manufactured in an area and that is particularly suitable for electrode applications.
- the inventors of the present application have come up with a method of electroplating aluminum on the surface of a resin molded body such as polyurethane or melamine. That is, the present invention forms a conductive layer made of one or more metals selected from the group consisting of gold, silver, platinum, rhodium, ruthenium, palladium, nickel, copper, cobalt, iron and aluminum on the surface of the resin molded body. And a plating process for plating aluminum in a molten salt bath on the conductive resin molded body (first invention of the present application). As described above, conventionally, although aluminum plating has been performed on a metal surface, electroplating on the surface of a resin molded body has not been considered. By making the surface of the resin molded body conductive, it is characterized in that it can be plated with aluminum even in a molten salt bath and has found a structure suitable as a conductive layer.
- the conductive layer made of the above-described metal has a higher conductivity than that of other metal or carbon, and is suitable as a conductive layer. Moreover, these metals are easy to form a layer having a smooth surface. Furthermore, since these metal materials are difficult to oxidize and do not form an oxide layer that impairs the adhesion of aluminum plating, the plating step can be performed without any special treatment immediately before aluminum plating. From these things, it is suitable for forming a uniform and large-area aluminum plating layer even on the surface of a resin molded body having a complicated shape.
- a suitable thickness is 0.001 ⁇ m to 0.2 ⁇ m, preferably 0.01 ⁇ m to 0.1 ⁇ m.
- a step of attaching one or more metals selected from the group consisting of gold, silver, platinum, rhodium, ruthenium, palladium and aluminum to the surface of the resin molded body by a vapor phase method is preferably used (this application).
- Third invention The vapor phase method is suitable for smoothly forming a thin conductive layer.
- a step of attaching one or more metals selected from the group consisting of gold, silver, platinum, rhodium, ruthenium, palladium, nickel, copper, cobalt and iron to the surface of the resin molded body by electroless plating. It is also possible (the fourth invention of the present application).
- Electroless plating forms a substantially uniform conductive layer regardless of the position of the surface layer part or deep part of the whole molded product, even if it is a resin molded product with a complicated structure such as a porous material with a fine three-dimensional network structure. It is preferable in that it can be performed.
- the step of attaching the metal by immersing the resin molded body in a paint containing one or more metals selected from the group consisting of gold, silver, platinum, rhodium, ruthenium, palladium and aluminum, Is preferably used in the same manner as electroless plating (the fifth invention of the present application).
- an aluminum porous body by using a resin porous body having a three-dimensional network structure (the second invention of the present application).
- a resin porous body made of urethane or melamine is preferably used in that a resin porous body having a high porosity can be obtained, and an aluminum porous body suitable for electrode applications can be obtained (No. 6 of the present application). invention).
- an aluminum structure having a resin molded body layer provided with a metal layer on the surface is obtained.
- it may be used as a composite of resin and metal as it is, or when used as a metal structure without resin due to restrictions on the usage environment such as electrode application, May be removed.
- the finished aluminum structure becomes a structure including two metal layers, ie, a metal as a conductive layer and aluminum.
- a structure having various advantageous characteristics such as an increase in mechanical strength as compared with a structure made of only aluminum, and a structure according to the application can be obtained.
- copper has a characteristic that high conductivity can be obtained
- nickel, cobalt, and iron have a characteristic that magnetism can be imparted.
- the eighth invention of the present application it is preferable to use a method for producing an aluminum structure having a dissolving step of dissolving the conductive layer after the plating step (the eighth invention of the present application).
- the conductive layer can be dissolved by immersing it in acid, particularly concentrated nitric acid, which is an oxidizing acid, without dissolving the aluminum.
- Aluminum does not dissolve in acid to form a passive film in an oxidizing acid on the surface, while the metal used for the conductive layer dissolves.
- the inventors of the present application have also come up with a method of electroplating aluminum on the surface of a resin molded body such as polyurethane or melamine. That is, in the present invention, a conductive step of forming a conductive layer made of aluminum on the surface of a resin molded body, a step of forming a zinc coating by performing zinc substitution plating on the surface of the conductive layer, and the zinc coating are formed. And a plating step of plating aluminum in a molten salt bath on a resin molded body. (Tenth invention of this application)
- zinc replacement plating (zincate treatment) is performed after the conductive step.
- zinc displacement plating zinc is deposited while removing the oxide film of aluminum, so that the zinc film is formed with the oxide film being broken. Since the galvanizing treatment is a substitution reaction between aluminum and zinc, if the surface of aluminum is covered with zinc, the reaction is completed, and the zinc film is formed extremely thin. Therefore, the zinc film does not become thick and the purity of aluminum can be kept high. Since it is difficult to form a strong oxide film on the surface of zinc and an oxide layer that hinders the adhesion of aluminum plating is not formed, the plating process can be performed satisfactorily thereafter.
- the zinc displacement plating step is performed by immersing the resin molded body on which the conductive layer is formed in a zinc displacement plating treatment solution.
- the zinc-displacement plating solution is a solution in which zinc oxide is dissolved in a strong alkaline solution, and an oxide film on the aluminum surface, which is a conductive layer, is dissolved by an alkali component.
- a base material with a complicated shape such as a porous resin body having a three-dimensional network structure
- a portion where an oxide film is not formed as a minute defect on the surface of the conductive layer (aluminum layer) formed on the surface. Occurs.
- the temperature of the zinc displacement plating solution is lower than the normal treatment temperature to be 4 ° C. or higher and 15 ° C. or lower (the 11th invention of the present application).
- the temperature of the zinc displacement plating treatment solution 15 ° C. or lower the reaction becomes mild and it is possible to prevent the aluminum surface from being excessively dissolved.
- the processing temperature is lower than 4 ° C., the reaction rate is slowed down, and the manufacturing time is increased due to the longer processing time.
- the inventors of the present application have come up with a method of electroplating aluminum on the surface of a resin molded body such as polyurethane or melamine. That is, the present invention provides a conductive step for forming a conductive layer made of aluminum on the surface of a resin molded body, and one type selected from the group consisting of gold, silver, platinum, rhodium, ruthenium and palladium on the surface of the conductive layer. It is a manufacturing method of an aluminum structure provided with the process of attaching the above-mentioned noble metal, and the plating process of plating aluminum in the molten salt bath to the resin fabrication object to which the noble metal adhered. (Twelfth Invention of the Present Application)
- one or more noble metals selected from the group consisting of gold, silver, platinum, rhodium, ruthenium and palladium are attached to the surface of the conductive layer.
- a vapor phase method such as vapor deposition or sputtering can be used. In the vapor phase method, noble metal can be deposited without any problem even if a thin oxide film is formed on the surface of the underlying aluminum.
- the noble metal can be attached by electroless plating or application of a paint containing the noble metal. Since these noble metals are not easily oxidized and do not form an acid underlayer that inhibits the adhesion of aluminum plating, aluminum plating in molten salt can be performed satisfactorily thereafter. Moreover, since these noble metals are not easily ionized, they are rarely eluted from the electrode in the charge / discharge cycle of the battery, and even if they are contained in the electrode material, no problem occurs.
- the aluminum structure obtained by the above production method is a structure in which the surface in contact with the resin or the one surface on which the resin is removed is a noble metal and the other surface is aluminum.
- the component ratio of each metal is measured by dissolving an aluminum structure in aqua regia and using an ICP (inductively coupled plasma) emission spectrometer.
- the aluminum structure obtained by the above manufacturing method is an aluminum structure having an aluminum layer having a thickness of 1 ⁇ m to 100 ⁇ m as a metal layer, and the metal layer has an aluminum content of 80% by mass or more, nickel, copper, cobalt And the total amount of iron is 2 mass% or more and 20 mass% or less, and the aluminum structure which consists of remainder unavoidable impurities (this invention 15th invention).
- the aluminum structure obtained when the conductive layer is removed in the above manufacturing method is an aluminum structure having an aluminum layer with a thickness of 1 ⁇ m to 100 ⁇ m as a metal layer, and the metal layer is made of 98% aluminum. 0.0 mass% or more, the total amount of nickel, copper, cobalt and iron is 0.0001 mass% or more and less than 2 mass%, and the balance is an aluminum structure composed of inevitable impurities (the 16th invention of the present application).
- the aluminum structure obtained by the above manufacturing method is an aluminum structure having an aluminum layer with a thickness of 1 ⁇ m to 100 ⁇ m as a metal layer, and the aluminum layer as a whole excluding the resin has an aluminum purity of 98.0% or more, This is an aluminum structure in which the zinc content is 0.0001% or more and 2% or less, and the balance is inevitable impurities (the seventeenth invention of the present application).
- the aluminum structure obtained by the above-described manufacturing method is an aluminum structure having a noble metal layer inside, with the surface in contact with the resin or one surface on the side where the resin is removed and the other surface being aluminum. More specifically, the metal layer has a first aluminum layer having a thickness of 1 ⁇ m to 100 ⁇ m on one surface and a second aluminum layer having a thickness of 0.05 ⁇ m to 1 ⁇ m on the other surface.
- An aluminum structure having a noble metal layer between aluminum layers (the eighteenth invention of the present application).
- the aluminum purity is 99.0% by mass or more
- the total amount of gold, silver, platinum, rhodium, ruthenium and palladium is 0.001% by mass to 1.0% by mass
- the balance is It is an inevitable impurity (the 19th invention of the present application).
- the skeleton has a shape in which a metal layer is formed in a cylindrical shape around the cavity from which the resin is removed or the resin is removed, and the inner side of the cylindrical body is a noble metal surface and the outer side is an aluminum surface. .
- the components as the whole metal layer are as described above.
- the skeleton portion of the network structure has a triangular shape as a whole.
- the triangle is not a strict meaning and refers to a shape having approximately three apexes and having three curves as sides. Therefore, the shape of the aluminum structure formed by plating also has a structure in which the skeleton has a substantially triangular shape.
- a process of attaching at least one noble metal selected from the group consisting of gold, silver, platinum, rhodium, ruthenium and palladium by electroless plating is considered as a conductive method.
- a conductive layer having a relatively uniform thickness can be formed, and the conductivity is the same at all positions of the triangle.
- electrolysis concentrates on corners (triangular apex portions), and the top portion becomes thicker than the central portion of the triangular side. This makes it possible to realize the shape described above. With such a shape, the strength of the cylindrical skeleton structure is improved, and in applications such as battery electrodes, there is an advantage that the active material retainability is excellent.
- the present invention it is possible to plate aluminum on the surface of a resin molded body, particularly a porous resin molded body having a three-dimensional network structure, and a large area can be manufactured with a substantially uniform thick film.
- a method capable of obtaining a porous aluminum body suitable for electrode applications it is possible to provide a method capable of obtaining a porous aluminum body suitable for electrode applications.
- FIG. 1 is a flowchart showing a manufacturing process of an aluminum structure according to a first embodiment of the present invention.
- FIG. 2 is a schematic cross-sectional view illustrating a manufacturing process of the aluminum structure according to the first embodiment of the present invention.
- FIG. 3 is an enlarged surface photograph showing the structure of a urethane foam resin as an example of a porous resin molded body.
- FIG. 4 is a schematic diagram illustrating a skeleton cross section of an aluminum porous body.
- FIG. 5 is a diagram for explaining an example of an aluminum continuous plating process by molten salt plating.
- FIG. 6 is a schematic cross-sectional view showing a structural example in which an aluminum porous body is applied to a molten salt battery.
- FIG. 1 is a flowchart showing a manufacturing process of an aluminum structure according to a first embodiment of the present invention.
- FIG. 2 is a schematic cross-sectional view illustrating a manufacturing process of the aluminum structure according to the first embodiment of the present invention
- FIG. 7 is a schematic cross-sectional view showing a structural example in which an aluminum porous body is applied to an electric double layer capacitor. It is a flowchart which shows the manufacturing process of the aluminum structure of 2nd Embodiment by this invention. It is a SEM photograph of the aluminum porous body concerning the example of the 2nd embodiment by the present invention. It is a SEM photograph of the aluminum porous body concerning another example of the 2nd embodiment by the present invention. It is the photograph which observed the frame
- FIG. 13 is a flowchart showing manufacturing steps of the aluminum structure according to the third embodiment of the present invention.
- FIG. 14 is a cross-sectional SEM photograph of a porous aluminum body according to a third embodiment of the present invention.
- FIG. 15 is a flowchart showing manufacturing steps of the aluminum structure according to the fourth embodiment of the present invention.
- FIG. 1 is a flowchart showing a manufacturing process of an aluminum structure according to a first embodiment of the present invention.
- FIG. 2 schematically shows a state in which an aluminum structure is formed using a resin molded body as a core material corresponding to the flowchart. The flow of the entire manufacturing process will be described with reference to both drawings.
- preparation 101 of the base resin molded body is performed.
- FIG. 2A is an enlarged schematic view showing a part of a cross section of a resin in which the surface of a foamed resin molded body having continuous air holes is enlarged as an example of the base resin molded body. The pores are formed with the foamed resin molded body 1 as a skeleton.
- the surface 102 of the resin molded body is made conductive.
- the conductive layer 2 is thinly formed on the surface of the resin molded body 1 as shown in FIG.
- aluminum plating 103 in molten salt is performed to form an aluminum plating layer 3 on the surface of the resin molded body on which the conductive layer is formed (FIG. 2C).
- an aluminum structure in which the aluminum plating layer 3 is formed on the surface using the base resin molded body as a base material is obtained.
- the removal 104 of the base resin molded body may be performed.
- An aluminum structure (porous body) in which only the metal layer remains can be obtained by disassembling and disappearing the foamed resin molded body 1 (FIG. 2D).
- each step will be described in order.
- a porous resin molded body having a three-dimensional network structure and continuous air holes is prepared.
- Arbitrary resin can be selected as a raw material of a porous resin molding.
- the material include foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene.
- foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene.
- a resin molded article having an arbitrary shape can be selected as long as it has continuous pores (continuous vent holes). For example, what has a shape like a nonwoven fabric entangled with a fibrous resin can be used instead of the foamed resin molded article.
- the foamed resin molded article preferably has a porosity of 80% to 98% and a pore diameter of 50 ⁇ m to 500 ⁇ m.
- Foamed urethane and foamed melamine can be preferably used as a foamed resin molded article because they have high porosity, have pore connectivity and are excellent in thermal decomposability.
- Foamed urethane is preferable in terms of uniformity of pores and availability, and urethane foam is preferable in that a product having a small pore diameter is obtained.
- the porous resin molded body often has residues such as foaming agents and unreacted monomers in the foam production process, and it is preferable to perform a washing treatment for the subsequent steps.
- FIG. 3 shows one obtained by washing urethane foam as a pretreatment.
- the resin molded body forms a three-dimensional network as a skeleton, thereby forming continuous pores as a whole.
- the skeleton of the urethane foam has a substantially triangular shape in a cross section perpendicular to the extending direction.
- the porosity is defined by the following equation.
- Porosity (1 ⁇ (weight of porous material [g] / (volume of porous material [cm 3 ] ⁇ material density))) ⁇ 100 [%]
- a conductive layer made of at least one noble metal selected from the group consisting of gold, silver, platinum, rhodium, ruthenium and palladium is formed on the surface of the foamed resin molded body.
- the conductive layer can be formed by any method other than electroless plating, such as sputtering, gas phase methods such as plasma CVD, and coating.
- a vapor phase method such as a vapor deposition method can be preferably applied.
- the thickness of the conductive layer is 0.001 ⁇ m to 0.2 ⁇ m, preferably 0.01 ⁇ m to 0.1 ⁇ m.
- the thickness of the conductive layer is thinner than 0.001 ⁇ m, the electroconductivity is insufficient and the electroplating cannot be performed satisfactorily in the next step.
- the thickness exceeds 0.2 ⁇ m, the cost of the conductive step increases.
- electroless plating or the like can be used in order to form a uniform layer throughout the entire depth.
- the means for evaporating is not particularly limited, and a method of irradiating an electron beam with an electron gun, resistance heating, induction overheating, a laser method, or the like can be used.
- a method of irradiating an electron beam with an electron gun, resistance heating, induction overheating, a laser method, or the like can be used.
- the pressure of the inert gas to be introduced is 0.01 Pa or more. When the pressure of the inert gas is less than 0.01 Pa, the thin film is poorly attached and unattached portions are formed.
- the atmospheric gas upper limit of the inert gas varies depending on the raw material heating method (electron gun, resistance heating, etc.) to be used, but is preferably 1 Pa or less from the viewpoint of the amount of gas used and the film forming speed.
- argon gas can be suitably used as the inert gas.
- Argon gas is preferable because it exists in nature in a relatively large amount, is available at low cost, and has little adverse effect on the human body.
- an existing film forming apparatus may be used.
- a vacuum deposition apparatus having a film formation chamber that divides a film formation target, a support base and a heating container on which gold and a film formation target are respectively mounted, and an electron gun for heating gold. it can.
- a vacuum deposition apparatus it is easy to introduce an inert gas uniformly around the urethane that is the film formation target of the present invention, and the space around the urethane is partitioned, so the pressure of the inert gas is adjusted. It is preferable because it is easy.
- urethane is placed on a support base of a vacuum deposition apparatus, and gold, which is a thin film raw material, is placed on a heating container.
- gold which is a thin film raw material
- a heating container is placed on a heating container.
- an inert gas is introduced into the film formation chamber.
- the pressure of the inert gas introduced into the film formation chamber is adjusted to be 0.01 to 1 Pa.
- an electron beam is emitted from an electron gun to melt gold, and a gold thin film is deposited on urethane.
- Formation of aluminum layer molten salt plating
- electrolytic plating is performed in a molten salt to form an aluminum plating layer 3 on the surface of the resin molded body.
- a direct current is applied in a molten salt using a resin molded body having a conductive surface as a cathode and an aluminum plate having a purity of 99.99% as an anode.
- the thickness of the aluminum plating layer is 1 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 20 ⁇ m.
- an organic molten salt that is a eutectic salt of an organic halide and an aluminum halide, or an inorganic molten salt that is a eutectic salt of an alkali metal halide and an aluminum halide can be used.
- Use of an organic molten salt bath that melts at a relatively low temperature is preferable because plating can be performed without decomposing the resin molded body as a base material.
- the organic halide imidazolium salt, pyridinium salt and the like can be used. Of these, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) are preferable.
- the imidazolium salt a salt containing an imidazolium cation having an alkyl group at the 1,3-position is preferably used.
- aluminum chloride, 1-ethyl-3-methylimidazolium chloride (AlCl 3 -EMIC) based molten salt It is most preferably used because it is highly stable and hardly decomposes.
- plating is preferably performed in an inert gas atmosphere such as nitrogen or argon and in a sealed environment.
- an inert gas atmosphere such as nitrogen or argon
- the temperature of the plating bath is 10 ° C. to 60 ° C., preferably 25 ° C. to 45 ° C.
- FIG. 5 is a diagram schematically showing a configuration of an apparatus for continuously performing metal plating treatment on the belt-shaped resin.
- a configuration in which the belt-like resin 22 whose surface is made conductive is sent from the left to the right in the figure.
- the first plating tank 21 a includes a cylindrical electrode 24, a positive electrode 25 provided on the inner wall of the container, and a plating bath 23. By passing the strip-shaped resin 22 through the plating bath 23 along the cylindrical electrode 24, a uniform current can easily flow through the entire resin, and uniform plating can be obtained.
- the plating tank 21b is a tank for applying a thick and uniform plating, and is configured to be repeatedly plated in a plurality of tanks.
- Plating is performed by passing the belt-like resin 22 having a thin metal tank on the surface through a plating bath 28 while sequentially feeding it by an electrode roller 26 that also serves as a feed roller and an external power feeding negative electrode.
- an electrode roller 26 that also serves as a feed roller and an external power feeding negative electrode.
- an aluminum structure (aluminum porous body) having a resin molded body as a skeleton core is obtained.
- the resin and metal composite may be used as they are.
- the resin may be removed when it is used as a metal structure without resin due to restrictions on the use environment. Removal of the resin can be performed by any method such as decomposition (dissolution) with an organic solvent, molten salt, or supercritical water, and thermal decomposition.
- methods such as thermal decomposition at high temperature are simple, but involve oxidation of aluminum. Aluminum, unlike nickel or the like, is difficult to reduce once oxidized.
- a method of removing the resin by thermal decomposition in a molten salt described below is preferably used so that oxidation of aluminum does not occur.
- the thermal decomposition in the molten salt is performed by the following method.
- a foamed resin molded body with an aluminum plating layer having an aluminum plating layer formed on the surface is immersed in a molten salt, and heated while applying a negative potential to the aluminum layer to decompose the foamed resin molded body.
- a negative potential is applied while immersed in the molten salt, the oxidation reaction of aluminum can be prevented.
- heating temperature can be suitably selected according to the kind of foaming resin molding, in order not to melt aluminum, it is necessary to process at the temperature below melting
- a preferable temperature range is 500 ° C. or more and 600 ° C. or less.
- the amount of negative potential to be applied is on the minus side of the reduction potential of aluminum and on the plus side of the reduction potential of cations in the molten salt.
- molten salt used for the thermal decomposition of the resin a salt of an alkali metal or alkaline earth metal halide that makes the electrode potential of aluminum base can be used.
- a salt of an alkali metal or alkaline earth metal halide that makes the electrode potential of aluminum base can be used.
- LiCl lithium chloride
- KCl potassium chloride
- NaCl sodium chloride
- AlCl 3 aluminum chloride
- FIG. 4 is a schematic diagram showing the A-A ′ cross section of FIG.
- the aluminum layer composed of the conductive layer 2 and the aluminum plating layer 3 has a cylindrical skeleton structure, and the cavity 4 in the skeleton structure has a substantially triangular cross-sectional shape.
- the thickness (t1) including the conductive layer of the aluminum layer at the apex portion of the triangle is thicker than the thickness (t2) of the central portion of the triangular side.
- the skeleton structure has a substantially triangular cross-sectional shape, and the thickness of the aluminum layer at the apex portion of the triangle is thicker than the thickness of the aluminum layer at the central portion of the triangle. An aluminum structure is obtained.
- LiNiO 2 lithium cobaltate
- LiMn 2 O 4 lithium manganate
- LiNiO 2 lithium nickelate
- the active material is used in combination with a conductive additive and a binder.
- Conventional positive electrode materials for lithium ion batteries have an active material coated on the surface of an aluminum foil. In order to improve the battery capacity per unit area, the coating thickness of the active material is increased.
- the aluminum foil and the active material need to be in electrical contact with each other, so that the active material is used in a mixture with a conductive additive.
- the porous aluminum body of the present invention has a high porosity and a large surface area per unit area. Therefore, even if the active material is thinly supported on the surface of the porous body, the active material can be used effectively, the capacity of the battery can be improved, and the mixing amount of the conductive auxiliary agent can be reduced.
- a lithium ion battery uses the above positive electrode material as a positive electrode, graphite as the negative electrode, and organic electrolyte as the electrolyte.
- the energy density of the battery can be made higher than that of a conventional lithium ion battery.
- the metal material formed as the conductive layer other than aluminum remains, but these metals are not eluted in the charge / discharge cycle of the battery and do not cause a problem.
- the aluminum porous body can also be used as an electrode material for a molten salt battery.
- a metal compound capable of intercalating a cation of a molten salt serving as an electrolyte such as sodium chromate (NaCrO 2 ) or titanium disulfide (TiO 2 ) as an active material.
- the active material is used in combination with a conductive additive and a binder.
- a conductive auxiliary agent acetylene black or the like can be used.
- the binder polytetrafluoroethylene (PTFE) or the like can be used.
- PTFE polytetrafluoroethylene
- the aluminum porous body can also be used as a negative electrode material for a molten salt battery.
- an aluminum porous body is used as a negative electrode material
- sodium alone, an alloy of sodium and another metal, carbon, or the like can be used as an active material.
- the melting point of sodium is about 98 ° C., and the metal softens as the temperature rises. Therefore, it is preferable to alloy sodium with other metals (Si, Sn, In, etc.). Of these, an alloy of sodium and Sn is particularly preferable because it is easy to handle.
- Sodium or a sodium alloy can be supported on the surface of the porous aluminum body by a method such as electrolytic plating or hot dipping.
- a metal alloy (such as Si) to be alloyed with sodium is attached to the aluminum porous body by a method such as plating, and then charged in a molten salt battery to form a sodium alloy.
- FIG. 6 is a schematic cross-sectional view showing an example of a molten salt battery using the above-described battery electrode material.
- the molten salt battery includes a positive electrode 121 carrying a positive electrode active material on the surface of an aluminum skeleton part of an aluminum porous body, a negative electrode 122 carrying a negative electrode active material on the surface of the aluminum skeleton part of an aluminum porous body, and an electrolyte.
- a separator 123 impregnated with molten salt is housed in a case 127. Between the upper surface of the case 127 and the negative electrode, a pressing member 126 including a pressing plate 124 and a spring 125 that presses the pressing plate is disposed.
- the current collector (aluminum porous body) of the positive electrode 121 and the current collector (aluminum porous body) of the negative electrode 122 are connected to the positive electrode terminal 128 and the negative electrode terminal 129 by lead wires 130, respectively.
- molten salt As the electrolyte, various inorganic salts or organic salts that melt at the operating temperature can be used.
- alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca)
- strontium (Sr) and barium (Ba) can be used.
- the operating temperature of the battery can be made 90 ° C. or lower.
- the molten salt is used by impregnating the separator.
- a separator is for preventing a positive electrode and a negative electrode from contacting, and a glass nonwoven fabric, porous resin, etc. can be used for it.
- the above positive electrode, negative electrode, and separator impregnated with molten salt are stacked and housed in a case to be used as a battery.
- the aluminum porous body can also be used as an electrode material for an electric double layer capacitor.
- activated carbon or the like is used as an electrode active material.
- Activated carbon is used in combination with a conductive additive and a binder.
- a conductive aid graphite, carbon nanotubes, and the like can be used.
- the binder polytetrafluoroethylene (PTFE), styrene butadiene rubber or the like can be used.
- FIG. 7 is a schematic cross-sectional view showing an example of an electric double layer capacitor using the above electrode material for an electric double layer capacitor.
- an electrode material in which an electrode active material is supported on a porous aluminum body is disposed as a polarizable electrode 141.
- the electrode material 141 is connected to the lead wire 144, and the whole is housed in the case 145.
- an aluminum porous body as a current collector, the surface area of the current collector is increased, and an electric double layer capacitor capable of high output and high capacity can be obtained even when activated carbon as an active material is thinly applied. .
- the present invention is not limited to the foamed resin molded body, and an aluminum structure having an arbitrary shape can be obtained by using the resin molded body having an arbitrary shape. Can be obtained.
- Example 1 a production example of the aluminum porous body will be specifically described.
- a foamed resin molding a urethane foam having a thickness of 1.6 mm, a porosity of 95%, and a pore number of about 20 per 1 cm was prepared and cut into 140 mm ⁇ 340 mm.
- a conductive layer having a thickness of 0.02 ⁇ m was formed by vapor-depositing gold on the surface of the urethane foam by a vapor deposition method.
- the means for evaporating gold was a method of irradiating an electron beam with an electron gun.
- An inert gas was introduced in the range of 0.01 to 1 Pa around the urethane, and gold was melted by an electron beam to deposit a gold thin film on the urethane.
- a urethane foam having a conductive layer formed on the surface was set in a jig having a power feeding function.
- the jig can feed power from four sides of the urethane foam and can be plated in an area of 100 mm ⁇ 300 mm.
- the set urethane foam was put in a glove box having an argon atmosphere and low moisture (dew point ⁇ 30 ° C. or lower) and immersed in a molten salt aluminum plating bath (67 mol% AlCl 3 -33 mol% EMIC) at a temperature of 40 ° C.
- a jig in which urethane foam was set was connected to the cathode side of the rectifier, and a counter aluminum plate (purity 99.99%) was connected to the anode side.
- the jig is provided with electrodes on four sides so that power can be supplied from four sides of the urethane foam.
- a direct current with a current density of 3.6 A / dm 2 was applied for 60 minutes to plate aluminum. Stirring was performed with a stirrer using a Teflon (registered trademark) rotor.
- Teflon registered trademark
- the apparent area of the porous aluminum body is used (the actual surface area of the urethane foam is about 8 times the apparent area).
- an aluminum plating film having a weight of 120 g / m 2 could be formed almost uniformly.
- the foamed resin on which the aluminum plating layer was formed was immersed in a LiCl—KCl eutectic molten salt at a temperature of 500 ° C., and a negative potential of ⁇ 1 V was applied for 30 minutes. It was estimated that bubbles were generated in the molten salt and the polyurethane decomposition reaction occurred. Then, after cooling to room temperature in the air, the molten salt was removed by washing with water to obtain a porous aluminum body.
- the obtained aluminum porous body was dissolved in aqua regia and measured with an ICP (inductively coupled plasma) emission spectrometer.
- the aluminum purity was 91.5 wt%, 8% gold, 0.5 wt% carbon. Was included.
- EDX analysis of the surface at an acceleration voltage of 15 kV almost no oxygen peak was observed, and it was confirmed that the oxygen content of the aluminum porous body was below the EDX detection limit (3.1 mass%). .
- a paste was prepared. The paste was filled in a porous aluminum body having a three-dimensional network structure and having a porosity of about 95%, and then vacuum-dried at 150 ° C., and further roll-pressed until the thickness became 70% of the initial thickness. Positive electrode) was prepared. This battery electrode material was punched out to 10 mm ⁇ , and fixed to a SUS304 coin battery container by spot welding. The positive electrode filling capacity was 2.4 mAh.
- LiCoO 2 , carbon black, and PVdF mixed paste were applied onto an aluminum foil having a thickness of 20 ⁇ m, and dried and roll-pressed in the same manner as described above to produce a battery electrode material (positive electrode).
- This battery electrode material was punched out to 10 mm ⁇ , and fixed to a SUS304 coin battery container by spot welding.
- the positive electrode filling capacity was 0.24 mAh.
- a polypropylene porous membrane having a thickness of 25 ⁇ m was used as a separator, and an EC / DEC (volume ratio 1: 1) solution in which 1M concentration of LiPF 6 was dissolved was added dropwise at 0.1 ml / cm 2 to the separator, and vacuum was applied. Impregnated.
- a lithium aluminum foil having a thickness of 20 ⁇ m and 11 mm ⁇ was used as the negative electrode, and was bonded and fixed to the upper cover of the coin battery container.
- the battery electrode material (positive electrode), separator, and negative electrode were laminated in this order, and a Viton O-ring was sandwiched between the upper lid and the lower lid to produce a battery.
- the upper limit voltage during charging and discharging was 4.2 V
- the lower limit voltage was 3.0 V
- discharging was performed at each discharge rate.
- the lithium secondary battery using the aluminum porous body as the positive electrode material had a capacity of about 5 times at a rate of 0.2 C compared with a conventional lithium foil battery electrode material.
- the problem of a short circuit was not seen also in the life test of the lithium ion battery.
- a life cycle test was performed based on the cycle life described in JIS C 8711.
- the upper limit voltage at the time of charging / discharging was 4.2V
- the lower limit voltage was 3.0V
- the cycle of discharging at a discharge rate of 0.2C was repeated.
- the lithium secondary battery using a porous aluminum body as a positive electrode material has no particular decrease in voltage or capacity, and no problem in the cycle characteristics, compared to a conventional aluminum foil electrode material. .
- FIG. 8 is a flowchart showing a manufacturing process of the aluminum structure according to the second embodiment of the present invention.
- an aluminum structure having an aluminum plating layer 3 formed on the surface using a base resin molded body as a base material is obtained in the same manner as in the first embodiment of the present invention.
- the removal 104 of the base resin molded body may be performed.
- the conductive layer removal 105 may be performed depending on the application.
- An aluminum structure (porous body) in which only the metal layer remains can be obtained by disassembling and disappearing the foamed resin molded body 1.
- each step will be described in order.
- a porous resin molded body having a three-dimensional network structure and continuous vents is prepared in the same manner as in the first embodiment of the present invention.
- Arbitrary resin can be selected as a raw material of a porous resin molding.
- the material include foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene.
- a conductive layer made of one or more metals selected from the group consisting of nickel, copper, cobalt, and iron is formed on the surface of the foamed resin molded body.
- the conductive layer can be formed by any method other than electroless plating, such as vapor deposition, sputtering, plasma CVD, etc., and coating.
- a vapor phase method such as a vapor deposition method can be preferably applied.
- electroless plating is preferable in order to form a uniform layer over the entire depth as the thickness increases.
- the thickness of the conductive layer is 0.01 ⁇ m to 1 ⁇ m, preferably 0.1 ⁇ m to 0.5 ⁇ m.
- the thickness of the conductive layer is smaller than 0.01 ⁇ m, the electroconductivity is insufficient and the electroplating cannot be performed satisfactorily in the next step.
- the thickness exceeds 1 ⁇ m, the cost of the conductive step increases.
- the method of electroless plating is not limited.
- a case where nickel is plated on a urethane foam is shown as an example.
- a colloidal catalyst composed of palladium chloride and tin chloride is adsorbed on the urethane surface.
- Sn is removed with sulfuric acid to activate the catalyst.
- it can immerse in the nickel plating liquid which uses hypophosphorous acid as a reducing agent, and can perform nickel electroless plating.
- hypophosphorous acid as a reducing agent
- phosphorus inevitably co-deposits to form a phosphorus alloy.
- Formation of aluminum layer molten salt plating
- electrolytic plating is performed in a molten salt to form an aluminum plating layer 3 on the surface of the resin molded body.
- a direct current is applied in a molten salt using a resin molded body having a conductive surface as a cathode and an aluminum plate having a purity of 99.99% as an anode.
- the thickness of the aluminum plating layer is 1 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 20 ⁇ m.
- an organic molten salt that is a eutectic salt of an organic halide and an aluminum halide, or an inorganic molten salt that is a eutectic salt of an alkali metal halide and an aluminum halide can be used.
- Use of an organic molten salt bath that melts at a relatively low temperature is preferable because plating can be performed without decomposing the resin molded body as a base material.
- the organic halide imidazolium salt, pyridinium salt and the like can be used. Of these, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) are preferable.
- the imidazolium salt a salt containing an imidazolium cation having an alkyl group at the 1,3-position is preferably used.
- aluminum chloride, 1-ethyl-3-methylimidazolium chloride (AlCl 3 -EMIC) based molten salt It is most preferably used because it is highly stable and hardly decomposes.
- plating is preferably performed in an inert gas atmosphere such as nitrogen or argon and in a sealed environment.
- an inert gas atmosphere such as nitrogen or argon
- the temperature of the plating bath is 10 ° C. to 60 ° C., preferably 25 ° C. to 45 ° C.
- an organic solvent is particularly preferably used as the organic solvent. Addition of an organic solvent, particularly xylene, can provide effects peculiar to the formation of an aluminum porous body. That is, the first feature that the aluminum skeleton forming the porous body is not easily broken and the second feature that uniform plating with a small difference in plating thickness between the surface portion and the inside of the porous body can be obtained. .
- the first feature is that by adding an organic solvent, the plating on the surface of the skeleton is improved from a granular shape (large irregularities look like particles in surface observation) to a flat shape, so that the thin skeleton is thin and strong. It will be.
- the second feature is that by adding an organic solvent to the molten salt bath, the viscosity of the molten salt bath decreases, and the plating bath easily flows into the fine network structure. That is, if the viscosity is high, a new plating bath is easily supplied to the surface of the porous body, and conversely, it is difficult to supply inside, but by reducing the viscosity, the plating bath is also easily supplied to the inside, It is possible to perform plating with a uniform thickness.
- the amount of the organic solvent added to the plating bath is preferably 25 to 57 mol%. If it is 25 mol% or less, it is difficult to obtain the effect of reducing the thickness difference between the surface layer and the inside. If it is 57 mol% or more, the plating bath becomes unstable and the plating solution and xylene are partially separated.
- the method further includes a cleaning step using the organic solvent as a cleaning liquid after the step of plating with the molten salt bath to which the organic solvent is added.
- the surface of the plated resin needs to be washed to wash away the plating bath.
- Such washing after plating is usually performed with water.
- water in the imidazolium salt bath, it is essential to avoid moisture.
- water is brought into the plating solution in the form of water vapor. Therefore, it is desirable to avoid washing with water in order to prevent adverse effects on the plating. Therefore, cleaning with an organic solvent is effective.
- an organic solvent is added to the plating bath as described above, a further advantageous effect can be obtained by washing with the organic solvent added to the plating bath.
- the washed plating solution can be collected and reused relatively easily, and the cost can be reduced.
- a plated body to which a bath in which xylene is added to molten salt AlCl 3 -EMIC is adhered is washed with xylene.
- the washed liquid becomes a liquid containing more xylene than the plating bath used.
- the molten salt AlCl 3 -EMIC is not mixed with a certain amount or more in xylene, and is separated from the molten salt AlCl 3 -EMIC containing xylene on the upper side and about 57 mol% xylene on the lower side.
- the molten liquid can be recovered by pumping the liquid on the side. Furthermore, since the boiling point of xylene is as low as 144 ° C., it is possible to adjust the xylene concentration in the recovered molten salt to the concentration in the plating solution and reuse it by applying heat. In addition, after washing
- FIG. 5 is a diagram schematically showing a configuration of an apparatus for continuously performing metal plating treatment on the belt-shaped resin.
- a configuration in which the belt-like resin 22 whose surface is made conductive is sent from the left to the right in the figure.
- the first plating tank 21 a includes a cylindrical electrode 24, a positive electrode 25 provided on the inner wall of the container, and a plating bath 23. By passing the strip-shaped resin 22 through the plating bath 23 along the cylindrical electrode 24, a uniform current can easily flow through the entire resin, and uniform plating can be obtained.
- the plating tank 21b is a tank for applying a thick and uniform plating, and is configured to be repeatedly plated in a plurality of tanks.
- Plating is performed by passing the belt-like resin 22 having a thin metal tank on the surface through a plating bath 28 while sequentially feeding it by an electrode roller 26 that also serves as a feed roller and an external power feeding negative electrode.
- an electrode roller 26 that also serves as a feed roller and an external power feeding negative electrode.
- an aluminum structure (aluminum porous body) having a resin molded body as a skeleton core is obtained.
- the resin and metal composite may be used as they are.
- the resin may be removed when it is used as a metal structure without resin due to restrictions on the use environment. Removal of the resin can be performed by any method such as decomposition (dissolution) with an organic solvent, molten salt, or supercritical water, and thermal decomposition.
- methods such as thermal decomposition at high temperature are simple, but involve oxidation of aluminum. Aluminum, unlike nickel or the like, is difficult to reduce once oxidized.
- a method of removing the resin by thermal decomposition in a molten salt described below is preferably used so that oxidation of aluminum does not occur.
- the thermal decomposition in the molten salt is performed by the following method.
- a foamed resin molded body with an aluminum plating layer having an aluminum plating layer formed on the surface is immersed in a molten salt, and heated while applying a negative potential to the aluminum layer to decompose the foamed resin molded body.
- a negative potential is applied while immersed in the molten salt, the oxidation reaction of aluminum can be prevented.
- heating temperature can be suitably selected according to the kind of foaming resin molding, in order not to melt aluminum, it is necessary to process at the temperature below melting
- a preferable temperature range is 500 ° C. or more and 600 ° C. or less.
- the amount of negative potential to be applied is on the minus side of the reduction potential of aluminum and on the plus side of the reduction potential of cations in the molten salt.
- molten salt used for the thermal decomposition of the resin a salt of an alkali metal or alkaline earth metal halide that makes the electrode potential of aluminum base can be used.
- a salt of an alkali metal or alkaline earth metal halide that makes the electrode potential of aluminum base can be used.
- LiCl lithium chloride
- KCl potassium chloride
- NaCl sodium chloride
- AlCl 3 aluminum chloride
- FIG. 4 is a schematic diagram showing the A-A ′ cross section of FIG.
- the aluminum layer composed of the conductive layer 2 and the aluminum plating layer 3 has a cylindrical skeleton structure, and the cavity 4 in the skeleton structure has a substantially triangular cross-sectional shape.
- the thickness (t1) of the aluminum layer at the apex portion of the triangle is thicker than the thickness (t2) of the aluminum layer at the center portion of the triangular side.
- the skeleton structure has a substantially triangular cross-sectional shape, and the thickness of the aluminum layer at the apex portion of the triangle is thicker than the thickness of the aluminum layer at the central portion of the triangle. An aluminum structure is obtained.
- the conductive layer is dissolved by immersing it in an acid, particularly concentrated nitric acid, which is an oxidizing acid, by removing the conductive layer without dissolving aluminum.
- an acid particularly concentrated nitric acid, which is an oxidizing acid
- Aluminum does not dissolve in acid to form a passive film in an oxidizing acid on the surface, while the metal used for the conductive layer dissolves.
- nickel when nickel is used as the conductive layer, it may be immersed in concentrated nitric acid 67.5% at 15 ° C. to 35 ° C. for 1 to 30 minutes, then washed with water and dried. Even when another metal is used as the conductive layer, it is only necessary to select and use an acid that dissolves.
- LiNiO 2 lithium cobaltate
- LiMn 2 O 4 lithium manganate
- LiNiO 2 lithium nickelate
- the active material is used in combination with a conductive additive and a binder.
- Conventional positive electrode materials for lithium ion batteries have an active material coated on the surface of an aluminum foil. In order to improve the battery capacity per unit area, the coating thickness of the active material is increased.
- the aluminum foil and the active material need to be in electrical contact with each other, so that the active material is used in a mixture with a conductive additive.
- the porous aluminum body of the present invention has a high porosity and a large surface area per unit area. Therefore, even if the active material is thinly supported on the surface of the porous body, the active material can be used effectively, the capacity of the battery can be improved, and the mixing amount of the conductive auxiliary agent can be reduced.
- a lithium ion battery uses the above positive electrode material as a positive electrode, graphite as the negative electrode, and organic electrolyte as the electrolyte. Since such a lithium ion battery can improve capacity even with a small electrode area, the energy density of the battery can be made higher than that of a conventional lithium ion battery.
- the aluminum porous body can also be used as an electrode material for a molten salt battery.
- a metal compound capable of intercalating a cation of a molten salt serving as an electrolyte such as sodium chromate (NaCrO 2 ) or titanium disulfide (TiO 2 ) as an active material.
- the active material is used in combination with a conductive additive and a binder.
- a conductive auxiliary agent acetylene black or the like can be used.
- the binder polytetrafluoroethylene (PTFE) or the like can be used.
- PTFE polytetrafluoroethylene
- the aluminum porous body can also be used as a negative electrode material for a molten salt battery.
- an aluminum porous body is used as a negative electrode material
- sodium alone, an alloy of sodium and another metal, carbon, or the like can be used as an active material.
- the melting point of sodium is about 98 ° C., and the metal softens as the temperature rises. Therefore, it is preferable to alloy sodium with other metals (Si, Sn, In, etc.). Of these, an alloy of sodium and Sn is particularly preferable because it is easy to handle.
- Sodium or a sodium alloy can be supported on the surface of the porous aluminum body by a method such as electrolytic plating or hot dipping.
- a metal alloy (such as Si) to be alloyed with sodium is attached to the aluminum porous body by a method such as plating, and then charged in a molten salt battery to form a sodium alloy.
- FIG. 6 is a schematic cross-sectional view showing an example of a molten salt battery using the above-described battery electrode material.
- the molten salt battery includes a positive electrode 121 carrying a positive electrode active material on the surface of an aluminum skeleton part of an aluminum porous body, a negative electrode 122 carrying a negative electrode active material on the surface of the aluminum skeleton part of an aluminum porous body, and an electrolyte.
- a separator 123 impregnated with molten salt is housed in a case 127. Between the upper surface of the case 127 and the negative electrode, a pressing member 126 including a pressing plate 124 and a spring 125 that presses the pressing plate is disposed.
- the current collector (aluminum porous body) of the positive electrode 121 and the current collector (aluminum porous body) of the negative electrode 122 are connected to the positive electrode terminal 128 and the negative electrode terminal 129 by lead wires 130, respectively.
- molten salt As the electrolyte, various inorganic salts or organic salts that melt at the operating temperature can be used.
- alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca)
- strontium (Sr) and barium (Ba) can be used.
- the operating temperature of the battery can be made 90 ° C. or lower.
- the molten salt is used by impregnating the separator.
- a separator is for preventing a positive electrode and a negative electrode from contacting, and a glass nonwoven fabric, porous resin, etc. can be used for it.
- the above positive electrode, negative electrode, and separator impregnated with molten salt are stacked and housed in a case to be used as a battery.
- the aluminum porous body can also be used as an electrode material for an electric double layer capacitor.
- activated carbon or the like is used as an electrode active material.
- Activated carbon is used in combination with a conductive additive and a binder.
- a conductive aid graphite, carbon nanotubes, and the like can be used.
- the binder polytetrafluoroethylene (PTFE), styrene butadiene rubber or the like can be used.
- FIG. 7 is a schematic cross-sectional view showing an example of an electric double layer capacitor using the above electrode material for an electric double layer capacitor.
- an electrode material in which an electrode active material is supported on a porous aluminum body is disposed as a polarizable electrode 141.
- the electrode material 141 is connected to the lead wire 144, and the whole is housed in the case 145.
- an aluminum porous body as a current collector, the surface area of the current collector is increased, and an electric double layer capacitor capable of high output and high capacity can be obtained even when activated carbon as an active material is thinly applied. .
- the present invention is not limited to the foamed resin molded body, and an aluminum structure having an arbitrary shape can be obtained by using the resin molded body having an arbitrary shape. Can be obtained.
- Example 2 a production example of the aluminum porous body will be specifically described.
- a foamed resin molding a urethane foam having a thickness of 1 mm, a porosity of 95%, and a number of pores (number of cells) per inch of about 50 was prepared and cut into 140 mm ⁇ 340 m.
- Electroless nickel plating was performed on the surface of the urethane foam to form a conductive layer.
- the urethane foam having a conductive layer formed on the surface was set in a jig having a power feeding function, and then immersed in a molten salt aluminum plating bath (17 mol% EMIC-34 mol% AlCl 3 -49 mol% xylene) at a temperature of 40 ° C.
- a jig in which urethane foam was set was connected to the cathode side of the rectifier, and a counter aluminum plate (purity 99.99%) was connected to the anode side.
- a direct current with a current density of 3.6 A / dm 2 was applied for 60 minutes to plate aluminum.
- FIG. 9 SEM photographs of the obtained porous aluminum body are shown in FIG. 9 (plating 1) and FIG. 10 (plating 2).
- FIG. 10 SEM photographs of the obtained porous aluminum body are shown in FIG. 9 (plating 1) and FIG. 10 (plating 2).
- the surface unevenness is relatively large, and especially in the vicinity of the skeleton ridgeline, the plating appears to grow in granular form, whereas in the plating containing xylene (FIG. 9) It can be seen that the surface is very smooth.
- FIG. 9 is a cross-sectional view obtained by cutting the porous aluminum body of FIG. 9 obtained by molten salt plating 1 along a plane parallel to the thickness direction
- FIG. 12 is a similar cross-section of the porous aluminum body of FIG. Show.
- the vertical direction is the thickness direction of the porous body
- the upper part surrounded by a dotted line is the front side
- the central part is the central part
- the lower part is the back side.
- front and back there is no distinction between front and back, and one surface is temporarily called the front surface and the other surface is temporarily called the back surface.
- the dotted line area is also meant to give an approximate distinction for explanation, and there is no particular boundary.
- the aluminum layer formed on the surface is visible as a substantially triangular cross section.
- the aluminum layer is uniformly formed as a whole as compared with FIG. That is, in FIG. 11, even if each side of one substantially triangular cross section is taken, the top portion is slightly more uniform than the side portion although it is slightly thicker than the side portion.
- the surface side, center part, and back side in the thickness direction of the entire porous body are compared, there is almost no difference in plating thickness. This corresponds to a very smooth skeleton surface in surface observation.
- the plating thickness in the vicinity of the top of the substantially triangular cross section is very thick, and this appears to be a granular lump by surface observation. Also, the plating thickness is thinner at the center than on the front and back sides.
- the foamed resin on which the aluminum plating layer was formed was immersed in a LiCl—KCl eutectic molten salt at a temperature of 500 ° C., and a negative potential of ⁇ 1 V was applied for 30 minutes. It was estimated that bubbles were generated in the molten salt and the polyurethane decomposition reaction occurred. Then, after cooling to room temperature in the air, the molten salt was removed by washing with water to obtain a porous aluminum body.
- the obtained aluminum porous body was immersed in 67.5% concentrated nitric acid at room temperature for 5 minutes, washed with water and dried to dissolve nickel as a conductive layer. Concentrated nitric acid dissolves nickel, but aluminum forms a passive film in the oxidizing acid on the surface, so it does not dissolve in the acid. Thereby, nickel is almost removed and an aluminum porous body with high aluminum purity can be obtained.
- the aluminum purity was 98.25 wt%, 0.7% nickel, 0.05% Of phosphorus and 1.0 wt% carbon. Furthermore, as a result of EDX analysis of the surface with an acceleration voltage of 15 kV, almost no oxygen peak was observed, and it was confirmed that the oxygen content of the aluminum porous body was below the EDX detection limit (3.1 mass%).
- a paste was prepared. The paste is filled in a porous aluminum body having a three-dimensional network structure and having a porosity of about 95%, and then vacuum-dried at 150 ° C., and further roll-pressed until the thickness reaches 70% of the initial thickness. (Positive electrode) was produced. This battery electrode material was punched out to 10 mm ⁇ , and fixed to a SUS304 coin battery container by spot welding. The positive electrode filling capacity was 2.4 mAh.
- LiCoO 2 , carbon black, and PVdF mixed paste were applied onto an aluminum foil having a thickness of 20 ⁇ m, and dried and roll-pressed in the same manner as described above to produce a battery electrode material (positive electrode).
- This battery electrode material was punched out to 10 mm ⁇ , and fixed to a SUS304 coin battery container by spot welding.
- the positive electrode filling capacity was 0.24 mAh.
- a polypropylene porous membrane having a thickness of 25 ⁇ m was used as a separator, and an EC / DEC (volume ratio 1: 1) solution in which 1M concentration of LiPF 6 was dissolved was added dropwise at 0.1 ml / cm 2 to the separator, and vacuum was applied. Impregnated.
- a lithium aluminum foil having a thickness of 20 ⁇ m and 11 mm ⁇ was used as the negative electrode, and was bonded and fixed to the upper cover of the coin battery container.
- the battery electrode material (positive electrode), separator, and negative electrode were laminated in this order, and a Viton O-ring was sandwiched between the upper lid and the lower lid to produce a battery.
- the upper limit voltage during charging and discharging was 4.2 V
- the lower limit voltage was 3.0 V
- discharging was performed at each discharge rate.
- the lithium secondary battery using the aluminum porous body as the positive electrode material had a capacity of about 5 times at a rate of 0.2 C compared with a conventional lithium foil battery electrode material.
- the problem of a short circuit was not seen also in the life test of the lithium ion battery.
- a life cycle test was performed based on the cycle life described in JIS C 8711.
- the upper limit voltage at the time of charging / discharging was 4.2V
- the lower limit voltage was 3.0V
- the cycle of discharging at a discharge rate of 0.2C was repeated.
- the lithium secondary battery using an aluminum porous body as a positive electrode material has no particular decrease in voltage or capacity, and no problem in cycle characteristics is found, compared with a conventional lithium foil using an aluminum foil as an electrode material.
- FIG. 13 is a flowchart showing manufacturing steps of the aluminum structure according to the third embodiment of the present invention.
- an aluminum structure having an aluminum plating layer 3 formed on the surface using a base resin molded body as a base material is obtained in the same manner as in the first embodiment of the present invention.
- a thin conductive layer 2 made of aluminum is formed on the surface of the resin molded body 1.
- coat by zinc substitution plating on the conductive layer 2 surface is performed. Since the zinc coating is deposited very thinly, it is not shown in FIG.
- a porous resin molded body having a three-dimensional network structure and continuous vents is prepared in the same manner as in the first embodiment of the present invention.
- Arbitrary resin can be selected as a raw material of a porous resin molding.
- the material include foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene.
- a conductive layer made of aluminum is formed on the surface of the foamed resin molded body.
- the conductive layer can be formed by an arbitrary method such as vapor deposition, sputtering, gas phase method such as plasma CVD, or application of aluminum paint.
- a vapor deposition method is preferable because a thin film can be formed uniformly.
- the thickness of the conductive layer is 0.05 ⁇ m to 5 ⁇ m, preferably 0.1 ⁇ m to 3 ⁇ m. When the thickness of the conductive layer is less than 0.05 ⁇ m, the electroconductivity is insufficient and the electroplating cannot be performed satisfactorily in the next step. On the other hand, if the thickness of the conductive layer is too thin, a zinc film cannot be formed satisfactorily in the zinc displacement plating process. If the thickness exceeds 5 ⁇ m, the cost of the conductive step increases.
- the conductive treatment may be performed by immersing the foamed resin molded body in a paint containing aluminum.
- a paint containing aluminum for example, a liquid in which aluminum fine particles having a particle diameter of 10 nm to 1 ⁇ m are dispersed in water or an organic solvent can be used.
- the conductive layer can be formed by immersing the foamed resin in the paint and then heating to evaporate the solvent.
- the resin molded body on which the conductive layer is formed is immersed in a zinc substitution plating solution.
- a zinc substitution plating treatment solution an aqueous solution of sodium hydroxide and zinc oxide, or a solution of ferric chloride dissolved in an aqueous solution of sodium hydroxide and zinc oxide can be used.
- the temperature of the zinc substitution plating solution is high, the reactivity increases and aluminum may be dissolved excessively. Therefore, the temperature of the solution is preferably controlled in the range of 4 ° C to 15 ° C.
- a so-called double zincate treatment in which zinc substitution plating is repeated may be performed.
- the zinc coating is stripped with nitric acid or the like, and zinc substitution plating is performed again.
- the double zincate treatment is performed, a zinc film having a dense structure can be formed, the adhesion between the conductive layer and the plating layer can be improved, and the elution of zinc from the aluminum structure can be suppressed.
- Formation of aluminum layer molten salt plating
- electrolytic plating is performed in a molten salt to form an aluminum plating layer 3 on the surface of the resin molded body.
- a direct current is applied in a molten salt using a resin molded body having a conductive surface as a cathode and an aluminum plate having a purity of 99.99% as an anode.
- the thickness of the aluminum plating layer is 1 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 20 ⁇ m.
- a direct current is applied in the molten salt with the resin molded body made conductive as a cathode and the counter electrode as an anode.
- an organic molten salt that is a eutectic salt of an organic halide and an aluminum halide, or an inorganic molten salt that is a eutectic salt of an alkali metal halide and an aluminum halide can be used.
- Use of an organic molten salt bath that melts at a relatively low temperature is preferable because plating can be performed without decomposing the resin molded body as a base material.
- the organic halide imidazolium salt, pyridinium salt and the like can be used. Of these, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) are preferable.
- the imidazolium salt a salt containing an imidazolium cation having an alkyl group at the 1,3-position is preferably used.
- aluminum chloride, 1-ethyl-3-methylimidazolium chloride (AlCl 3 -EMIC) based molten salt It is most preferably used because it is highly stable and hardly decomposes.
- plating is preferably performed in an inert gas atmosphere such as nitrogen or argon and in a sealed environment.
- an inert gas atmosphere such as nitrogen or argon
- the temperature of the plating bath is 10 ° C. to 60 ° C., preferably 25 ° C. to 45 ° C.
- FIG. 5 is a diagram schematically showing a configuration of an apparatus for continuously performing metal plating treatment on the belt-shaped resin.
- a configuration in which the belt-like resin 22 whose surface is made conductive is sent from the left to the right in the figure.
- the first plating tank 21 a includes a cylindrical electrode 24, a positive electrode 25 provided on the inner wall of the container, and a plating bath 23. By passing the strip-shaped resin 22 through the plating bath 23 along the cylindrical electrode 24, a uniform current can easily flow through the entire resin, and uniform plating can be obtained.
- the plating tank 21b is a tank for applying a thick and uniform plating, and is configured to be repeatedly plated in a plurality of tanks.
- Plating is performed by passing the belt-like resin 22 having a thin metal tank on the surface through a plating bath 28 while sequentially feeding it by an electrode roller 26 that also serves as a feed roller and an external power feeding negative electrode.
- an electrode roller 26 that also serves as a feed roller and an external power feeding negative electrode.
- an aluminum structure (aluminum porous body) having a resin molded body as a skeleton core is obtained.
- the resin and metal composite may be used as they are.
- the resin may be removed when it is used as a metal structure without resin due to restrictions on the use environment. Removal of the resin can be performed by any method such as decomposition (dissolution) with organic solvent, molten salt, or supercritical water, and thermal decomposition.
- methods such as thermal decomposition at high temperature are simple, but involve oxidation of aluminum.
- Aluminum, unlike nickel or the like, is difficult to reduce once oxidized.
- a method of removing the resin by thermal decomposition in a molten salt described below is preferably used so that oxidation of aluminum does not occur.
- Thermal decomposition in the molten salt is performed by the following method.
- a foamed resin molded body with an aluminum plating layer having an aluminum plating layer formed on the surface is immersed in a molten salt, and heated while applying a negative potential to the aluminum layer to decompose the foamed resin molded body.
- a negative potential is applied while immersed in the molten salt, the oxidation reaction of aluminum can be prevented.
- the foamed resin molded body can be decomposed without oxidizing aluminum.
- heating temperature can be suitably selected according to the kind of foaming resin molding, in order not to melt aluminum, it is necessary to process at the temperature below melting
- a preferable temperature range is 500 ° C. or more and 600 ° C. or less.
- the amount of negative potential to be applied is on the minus side of the reduction potential of aluminum and on the plus side of the reduction potential of cations in the molten salt.
- molten salt used for the thermal decomposition of the resin a salt of an alkali metal or alkaline earth metal halide that makes the electrode potential of aluminum base can be used.
- a salt of an alkali metal or alkaline earth metal halide that makes the electrode potential of aluminum base can be used.
- LiCl lithium chloride
- KCl potassium chloride
- NaCl sodium chloride
- AlCl 3 aluminum chloride
- FIG. 4 is a schematic diagram showing the A-A ′ cross section of FIG.
- the aluminum layer composed of the conductive layer 2 and the aluminum plating layer 3 has a cylindrical skeleton structure, and the cavity 4 in the skeleton structure has a substantially triangular cross-sectional shape.
- the thickness (t1) including the conductive layer of the aluminum layer at the apex portion of the triangle is thicker than the thickness (t2) of the central portion of the triangular side.
- the skeleton structure has a substantially triangular cross-sectional shape, and the thickness of the aluminum layer at the apex portion of the triangle is thicker than the thickness of the aluminum layer at the central portion of the triangle. An aluminum structure is obtained.
- LiNiO 2 lithium cobaltate
- LiMn 2 O 4 lithium manganate
- LiNiO 2 lithium nickelate
- the active material is used in combination with a conductive additive and a binder.
- Conventional positive electrode materials for lithium ion batteries have an active material coated on the surface of an aluminum foil. In order to improve the battery capacity per unit area, the coating thickness of the active material is increased.
- the aluminum foil and the active material need to be in electrical contact with each other, so that the active material is used in a mixture with a conductive additive.
- the porous aluminum body of the present invention has a high porosity and a large surface area per unit area. Therefore, even if the active material is thinly supported on the surface of the porous body, the active material can be used effectively, the capacity of the battery can be improved, and the mixing amount of the conductive auxiliary agent can be reduced.
- a lithium ion battery uses the above positive electrode material as a positive electrode, graphite as the negative electrode, and organic electrolyte as the electrolyte. Since such a lithium ion battery can improve capacity even with a small electrode area, the energy density of the battery can be made higher than that of a conventional lithium ion battery.
- the aluminum porous body can also be used as an electrode material for a molten salt battery.
- a metal compound capable of intercalating a cation of a molten salt serving as an electrolyte such as sodium chromate (NaCrO 2 ) or titanium disulfide (TiO 2 ) as an active material.
- the active material is used in combination with a conductive additive and a binder.
- a conductive auxiliary agent acetylene black or the like can be used.
- the binder polytetrafluoroethylene (PTFE) or the like can be used.
- PTFE polytetrafluoroethylene
- the aluminum porous body can also be used as a negative electrode material for a molten salt battery.
- an aluminum porous body is used as a negative electrode material
- sodium alone, an alloy of sodium and another metal, carbon, or the like can be used as an active material.
- the melting point of sodium is about 98 ° C., and the metal softens as the temperature rises. Therefore, it is preferable to alloy sodium with other metals (Si, Sn, In, etc.). Of these, an alloy of sodium and Sn is particularly preferable because it is easy to handle.
- Sodium or a sodium alloy can be supported on the surface of the porous aluminum body by a method such as electrolytic plating or hot dipping.
- a metal alloy (such as Si) to be alloyed with sodium is attached to the aluminum porous body by a method such as plating, and then charged in a molten salt battery to form a sodium alloy.
- FIG. 6 is a schematic cross-sectional view showing an example of a molten salt battery using the above-described battery electrode material.
- the molten salt battery includes a positive electrode 121 carrying a positive electrode active material on the surface of an aluminum skeleton part of an aluminum porous body, a negative electrode 122 carrying a negative electrode active material on the surface of the aluminum skeleton part of an aluminum porous body, and an electrolyte.
- a separator 123 impregnated with molten salt is housed in a case 127. Between the upper surface of the case 127 and the negative electrode, a pressing member 126 including a pressing plate 124 and a spring 125 that presses the pressing plate is disposed.
- the current collector (aluminum porous body) of the positive electrode 121 and the current collector (aluminum porous body) of the negative electrode 122 are connected to the positive electrode terminal 128 and the negative electrode terminal 129 by lead wires 130, respectively.
- molten salt As the electrolyte, various inorganic salts or organic salts that melt at the operating temperature can be used.
- alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca)
- strontium (Sr) and barium (Ba) can be used.
- the operating temperature of the battery can be made 90 ° C. or lower.
- the molten salt is used by impregnating the separator.
- a separator is for preventing a positive electrode and a negative electrode from contacting, and a glass nonwoven fabric, porous resin, etc. can be used for it.
- the above positive electrode, negative electrode, and separator impregnated with molten salt are stacked and housed in a case to be used as a battery.
- the aluminum porous body can also be used as an electrode material for an electric double layer capacitor.
- activated carbon or the like is used as an electrode active material.
- Activated carbon is used in combination with a conductive additive and a binder.
- a conductive aid graphite, carbon nanotubes, and the like can be used.
- the binder polytetrafluoroethylene (PTFE), styrene butadiene rubber or the like can be used.
- FIG. 7 is a schematic cross-sectional view showing an example of an electric double layer capacitor using the above electrode material for an electric double layer capacitor.
- an electrode material in which an electrode active material is supported on a porous aluminum body is disposed as a polarizable electrode 141.
- the electrode material 141 is connected to the lead wire 144, and the whole is housed in the case 145.
- an aluminum porous body as a current collector, the surface area of the current collector is increased, and an electric double layer capacitor capable of high output and high capacity can be obtained even when activated carbon as an active material is thinly applied. .
- the present invention is not limited to the foamed resin molded body, and an aluminum structure having an arbitrary shape can be obtained by using the resin molded body having an arbitrary shape. Can be obtained.
- Example Production of porous aluminum body: formation of aluminum layer by vapor deposition
- a production example of the aluminum porous body will be specifically described.
- a foamed resin molding a urethane foam having a thickness of 1.6 mm, a porosity of 95%, and a pore number of about 20 per 1 cm was prepared and cut into 140 mm ⁇ 190 mm squares.
- Aluminum was vapor-deposited on the surface of the urethane foam to form a conductive layer having a thickness of about 2.5 ⁇ m.
- urethane foam was set was connected to the cathode side of the rectifier, and a counter aluminum plate (purity 99.99%) was connected to the anode side.
- the jig can supply power from four sides of the urethane foam and can be plated on an area of 100 mm ⁇ 150 mm. It was immersed in a molten salt aluminum plating bath (67 mol% AlCl 3 -33 mol% EMIC) at a temperature of 40 ° C., and a direct current having a current density of 3.6 A / dm 2 was applied for 60 minutes to plate aluminum.
- the obtained porous aluminum body was dissolved in aqua regia and measured with an ICP (inductively coupled plasma) emission spectrometer.
- the carbon content was measured by a high frequency induction furnace combustion-infrared absorption method of JIS-G1211.
- the aluminum purity was 99.48% by mass and contained 0.5% by mass of carbon and 0.02% by mass of zinc.
- EDX analysis of the surface at an acceleration voltage of 15 kV almost no oxygen peak was observed, and it was confirmed that the oxygen content of the aluminum porous body was below the EDX detection limit (3.1 mass%).
- a paste was prepared. The paste is filled in a porous aluminum body having a three-dimensional network structure and having a porosity of about 95%, and then vacuum-dried at 150 ° C., and further roll-pressed until the thickness reaches 70% of the initial thickness. (Positive electrode) was produced. This battery electrode material was punched out to 10 mm ⁇ , and fixed to a SUS304 coin battery container by spot welding. The positive electrode filling capacity was 2.4 mAh.
- LiCoO 2 , carbon black, and PVdF mixed paste were applied onto an aluminum foil having a thickness of 20 ⁇ m, and dried and roll-pressed in the same manner as described above to produce a battery electrode material (positive electrode).
- This battery electrode material was punched out to 10 mm ⁇ , and fixed to a SUS304 coin battery container by spot welding.
- the positive electrode filling capacity was 0.24 mAh.
- a polypropylene porous membrane having a thickness of 25 ⁇ m was used as a separator, and an EC / DEC (volume ratio 1: 1) solution in which 1M concentration of LiPF 6 was dissolved was added dropwise at 0.1 ml / cm 2 to the separator, and vacuum was applied. Impregnated.
- a lithium aluminum foil having a thickness of 20 ⁇ m and 11 mm ⁇ was used as the negative electrode, and was bonded and fixed to the upper cover of the coin battery container.
- the battery electrode material (positive electrode), separator, and negative electrode were laminated in this order, and a Viton O-ring was sandwiched between the upper lid and the lower lid to produce a battery.
- the upper limit voltage during heavy discharge was 4.2 V
- the lower limit voltage was 3.0 V
- discharging was performed at each discharge rate.
- the lithium secondary battery using the aluminum porous body as the positive electrode material had a capacity of about 5 times at a rate of 0.2 C compared with a conventional lithium foil battery electrode material. Further, a life cycle test was performed based on the cycle life described in JIS C 8711.
- the upper limit voltage at the time of charging / discharging was 4.2V
- the lower limit voltage was 3.0V
- after charging to the positive electrode filling capacity, the cycle of discharging at a discharge rate of 0.2C was repeated.
- the lithium secondary battery using an aluminum porous body as a positive electrode material has no particular decrease in voltage or capacity, and no problem in cycle characteristics is found, compared with a conventional lithium foil using an aluminum foil as an electrode material.
- FIG. 15 is a flowchart which shows the manufacturing process of the aluminum structure of 4th Embodiment by this invention by this invention.
- FIG. 2 schematically shows a state in which an aluminum structure is formed using a resin molded body as a core material corresponding to the flowchart.
- a thin conductive layer 2 made of aluminum is formed on the surface of the resin molded body 1.
- the process 103 which adheres a noble metal to the surface of the conductive layer 2 is performed.
- the noble metal is not shown in FIG. 2 because it is deposited very thinly.
- a porous resin molded body having a three-dimensional network structure and continuous vents is prepared in the same manner as in the first embodiment of the present invention.
- Arbitrary resin can be selected as a raw material of a porous resin molding.
- the material include foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene.
- a conductive layer made of aluminum is formed on the surface of the foamed resin molded body.
- the conductive layer can be formed by an arbitrary method such as vapor deposition, sputtering, gas phase method such as plasma CVD, or application of aluminum paint.
- a vapor deposition method is preferable because a thin film can be formed uniformly.
- the thickness of the conductive layer is 0.05 ⁇ m to 1 ⁇ m, preferably 0.1 ⁇ m to 0.5 ⁇ m. When the thickness of the conductive layer is smaller than 0.01 ⁇ m, the electroconductivity is insufficient and the electroplating cannot be performed satisfactorily in the next step. On the other hand, when the thickness exceeds 1 ⁇ m, the cost of the conductive step increases.
- the conductive treatment may be performed by immersing the foamed resin molded body in a paint containing aluminum.
- a paint containing aluminum for example, a liquid in which aluminum fine particles having a particle diameter of 10 nm to 1 ⁇ m are dispersed in water or an organic solvent can be used.
- the conductive layer can be formed by immersing the foamed resin in the paint and then heating to evaporate the solvent.
- Platinum pretreatment Precious metal adhesion
- aluminum is plated by molten salt plating to form an aluminum plating layer.
- a noble metal is attached to the surface of the conductive layer (aluminum layer) before the plating step.
- the noble metal can be attached by an arbitrary method such as vapor deposition such as vapor deposition, sputtering, or plasma CVD, electroless plating, or coating of a coating containing noble metal.
- a vapor deposition method is preferable because a thin film can be formed uniformly. Since these noble metals are very expensive, they are preferably thin from the viewpoint of cost.
- the thickness of the noble metal layer is 0.0001 ⁇ m to 1 ⁇ m, preferably 0.001 ⁇ m to 0.01 ⁇ m. When the thickness of the noble metal layer is less than 0.0001 ⁇ m, the aluminum oxide film cannot be completely covered and good plating cannot be performed. When the thickness of the noble metal layer exceeds 1 ⁇ m, the cost of the conductive process increases.
- the means for evaporating is not particularly limited, and a method of irradiating an electron beam with an electron gun, resistance heating, induction overheating, a laser method, or the like can be used.
- an inert gas around the urethane with the conductive layer.
- the pressure of the inert gas to be introduced is 0.01 Pa or more. When the pressure of the inert gas is less than 0.01 Pa, the thin film is poorly attached and unattached portions are formed.
- the atmospheric gas upper limit of the inert gas varies depending on the raw material heating method (electron gun, resistance heating, etc.) to be used, but is preferably 1 Pa or less from the viewpoint of the amount of gas used and the film forming speed.
- argon gas can be suitably used as the inert gas.
- Argon gas is preferable because it exists in nature in a relatively large amount, is available at low cost, and has little adverse effect on the human body.
- an existing film forming apparatus may be used.
- a vacuum deposition apparatus having a film formation chamber that divides a film formation target, a support base and a heating container on which gold and a film formation target are respectively mounted, and an electron gun for heating gold. it can.
- a vacuum deposition apparatus it is easy to uniformly introduce an inert gas around the urethane with a conductive layer, which is a film formation target of the present invention, and the inert space because the space around the urethane with the conductive layer is partitioned. This is preferable because the gas pressure can be easily adjusted.
- the urethane with a conductive layer is placed on a support base of a vacuum deposition apparatus, and gold, which is a thin film raw material, is placed on a heating container.
- gold which is a thin film raw material
- the film formation chamber is evacuated to a high vacuum state, an inert gas is introduced into the film formation chamber.
- the pressure of the inert gas introduced into the film formation chamber is adjusted to be 0.01 to 1 Pa.
- an electron beam is emitted from an electron gun to melt gold, and a gold thin film is deposited on urethane.
- Formation of aluminum layer molten salt plating
- electrolytic plating is performed in a molten salt to form an aluminum plating layer 3 on the surface of the resin molded body.
- a direct current is applied in a molten salt using a resin molded body having a conductive surface as a cathode and an aluminum plate having a purity of 99.99% as an anode.
- the thickness of the aluminum plating layer is 1 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 20 ⁇ m.
- a direct current is applied in the molten salt using a conductive resin molded body as a cathode and a counter electrode as an anode.
- an organic molten salt that is a eutectic salt of an organic halide and an aluminum halide, or an inorganic molten salt that is a eutectic salt of an alkali metal halide and an aluminum halide can be used.
- Use of an organic molten salt bath that melts at a relatively low temperature is preferable because plating can be performed without decomposing the resin molded body as a base material.
- the organic halide imidazolium salt, pyridinium salt and the like can be used. Of these, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) are preferable.
- the imidazolium salt a salt containing an imidazolium cation having an alkyl group at the 1,3-position is preferably used.
- aluminum chloride, 1-ethyl-3-methylimidazolium chloride (AlCl 3 -EMIC) based molten salt It is most preferably used because it is highly stable and hardly decomposes.
- plating is preferably performed in an inert gas atmosphere such as nitrogen or argon and in a sealed environment.
- an inert gas atmosphere such as nitrogen or argon
- the temperature of the plating bath is 10 ° C. to 60 ° C., preferably 25 ° C. to 45 ° C.
- FIG. 5 is a diagram schematically showing a configuration of an apparatus for continuously performing metal plating treatment on the belt-shaped resin.
- a configuration in which the belt-like resin 22 whose surface is made conductive is sent from the left to the right in the figure.
- the first plating tank 21 a includes a cylindrical electrode 24, a positive electrode 25 provided on the inner wall of the container, and a plating bath 23. By passing the strip-shaped resin 22 through the plating bath 23 along the cylindrical electrode 24, a uniform current can easily flow through the entire resin, and uniform plating can be obtained.
- the plating tank 21b is a tank for applying a thick and uniform plating, and is configured to be repeatedly plated in a plurality of tanks.
- Plating is performed by passing the belt-like resin 22 having a thin metal tank on the surface through a plating bath 28 while sequentially feeding it by an electrode roller 26 that also serves as a feed roller and an external power feeding negative electrode.
- an electrode roller 26 that also serves as a feed roller and an external power feeding negative electrode.
- an aluminum structure (aluminum porous body) having a resin molded body as a skeleton core is obtained.
- the resin and metal composite may be used as they are.
- the resin may be removed when it is used as a metal structure without resin due to restrictions on the use environment. Removal of the resin can be performed by any method such as decomposition (dissolution) with an organic solvent, molten salt, or supercritical water, and thermal decomposition.
- methods such as thermal decomposition at high temperature are simple, but involve oxidation of aluminum. Aluminum, unlike nickel or the like, is difficult to reduce once oxidized.
- a method of removing the resin by thermal decomposition in a molten salt described below is preferably used so that oxidation of aluminum does not occur.
- Thermal decomposition in the molten salt is performed by the following method.
- a foamed resin molded body with an aluminum plating layer having an aluminum plating layer formed on the surface is immersed in a molten salt, and heated while applying a negative potential to the aluminum layer to decompose the foamed resin molded body.
- a negative potential is applied while immersed in the molten salt, the oxidation reaction of aluminum can be prevented.
- the foamed resin molded body can be decomposed without oxidizing aluminum.
- heating temperature can be suitably selected according to the kind of foaming resin molding, in order not to melt aluminum, it is necessary to process at the temperature below melting
- a preferable temperature range is 500 ° C. or more and 600 ° C. or less.
- the amount of negative potential to be applied is on the minus side of the reduction potential of aluminum and on the plus side of the reduction potential of cations in the molten salt.
- molten salt used for the thermal decomposition of the resin a salt of an alkali metal or alkaline earth metal halide that makes the electrode potential of aluminum base can be used.
- a salt of an alkali metal or alkaline earth metal halide that makes the electrode potential of aluminum base can be used.
- LiCl lithium chloride
- KCl potassium chloride
- NaCl sodium chloride
- AlCl 3 aluminum chloride
- FIG. 4 is a schematic diagram showing the A-A ′ cross section of FIG.
- the aluminum layer composed of the conductive layer 2 and the aluminum plating layer 3 has a cylindrical skeleton structure, and the cavity 4 in the skeleton structure has a substantially triangular cross-sectional shape.
- the thickness (t1) including the conductive layer of the aluminum layer at the apex portion of the triangle is thicker than the thickness (t2) of the central portion of the triangular side.
- the skeleton structure has a substantially triangular cross-sectional shape, and the thickness of the aluminum layer at the apex portion of the triangle is thicker than the thickness of the aluminum layer at the central portion of the triangle. An aluminum structure is obtained.
- a noble metal layer is formed between the conductive layer 2 and the aluminum plating layer 3. Since noble metals hardly cause oxidation-reduction reactions, when an aluminum structure is used as an electrode of a battery, it is less likely to be dissolved or deposited to cause deterioration of the battery. Further, the noble metal layer is inside the aluminum structure, and the surface portion in contact with the battery electrolyte has high aluminum purity, so that the battery is hardly deteriorated. Therefore, even if a trace amount of noble metal is contained in the aluminum structure, it can be used favorably as a battery electrode material. The total amount of gold, silver, platinum, rhodium, ruthenium and palladium is 0.001% to 1.0%. Note that the noble metal layer may diffuse into the aluminum through a heating step such as a resin decomposition step.
- LiNiO 2 lithium cobaltate
- LiMn 2 O 4 lithium manganate
- LiNiO 2 lithium nickelate
- the active material is used in combination with a conductive additive and a binder.
- Conventional positive electrode materials for lithium ion batteries have an active material coated on the surface of an aluminum foil. In order to improve the battery capacity per unit area, the coating thickness of the active material is increased.
- the aluminum foil and the active material need to be in electrical contact with each other, so that the active material is used in a mixture with a conductive additive.
- the porous aluminum body of the present invention has a high porosity and a large surface area per unit area. Therefore, even if the active material is thinly supported on the surface of the porous body, the active material can be used effectively, the capacity of the battery can be improved, and the mixing amount of the conductive auxiliary agent can be reduced.
- a lithium ion battery uses the above positive electrode material as a positive electrode, graphite as the negative electrode, and organic electrolyte as the electrolyte. Since such a lithium ion battery can improve capacity even with a small electrode area, the energy density of the battery can be made higher than that of a conventional lithium ion battery.
- the aluminum porous body can also be used as an electrode material for a molten salt battery.
- a metal compound capable of intercalating a cation of a molten salt serving as an electrolyte such as sodium chromate (NaCrO 2 ) or titanium disulfide (TiO 2 ) as an active material.
- the active material is used in combination with a conductive additive and a binder.
- a conductive auxiliary agent acetylene black or the like can be used.
- the binder polytetrafluoroethylene (PTFE) or the like can be used.
- PTFE polytetrafluoroethylene
- the aluminum porous body can also be used as a negative electrode material for a molten salt battery.
- an aluminum porous body is used as a negative electrode material
- sodium alone, an alloy of sodium and another metal, carbon, or the like can be used as an active material.
- the melting point of sodium is about 98 ° C., and the metal softens as the temperature rises. Therefore, it is preferable to alloy sodium with other metals (Si, Sn, In, etc.). Of these, an alloy of sodium and Sn is particularly preferable because it is easy to handle.
- Sodium or a sodium alloy can be supported on the surface of the porous aluminum body by a method such as electrolytic plating or hot dipping.
- a metal alloy (such as Si) to be alloyed with sodium is attached to the aluminum porous body by a method such as plating, and then charged in a molten salt battery to form a sodium alloy.
- FIG. 6 is a schematic cross-sectional view showing an example of a molten salt battery using the above-described battery electrode material.
- the molten salt battery includes a positive electrode 121 carrying a positive electrode active material on the surface of an aluminum skeleton part of an aluminum porous body, a negative electrode 122 carrying a negative electrode active material on the surface of the aluminum skeleton part of an aluminum porous body, and an electrolyte.
- a separator 123 impregnated with molten salt is housed in a case 127. Between the upper surface of the case 127 and the negative electrode, a pressing member 126 including a pressing plate 124 and a spring 125 that presses the pressing plate is disposed.
- the current collector (aluminum porous body) of the positive electrode 121 and the current collector (aluminum porous body) of the negative electrode 122 are connected to the positive electrode terminal 128 and the negative electrode terminal 129 by lead wires 130, respectively.
- molten salt As the electrolyte, various inorganic salts or organic salts that melt at the operating temperature can be used.
- alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca)
- strontium (Sr) and barium (Ba) can be used.
- the operating temperature of the battery can be made 90 ° C. or lower.
- the molten salt is used by impregnating the separator.
- a separator is for preventing a positive electrode and a negative electrode from contacting, and a glass nonwoven fabric, porous resin, etc. can be used for it.
- the above positive electrode, negative electrode, and separator impregnated with molten salt are stacked and housed in a case to be used as a battery.
- the aluminum porous body can also be used as an electrode material for an electric double layer capacitor.
- activated carbon or the like is used as an electrode active material.
- Activated carbon is used in combination with a conductive additive and a binder.
- a conductive aid graphite, carbon nanotubes, and the like can be used.
- the binder polytetrafluoroethylene (PTFE), styrene butadiene rubber or the like can be used.
- FIG. 7 is a schematic cross-sectional view showing an example of an electric double layer capacitor using the above electrode material for an electric double layer capacitor.
- an electrode material in which an electrode active material is supported on a porous aluminum body is disposed as a polarizable electrode 141.
- the electrode material 141 is connected to the lead wire 144, and the whole is housed in the case 145.
- an aluminum porous body as a current collector, the surface area of the current collector is increased, and an electric double layer capacitor capable of high output and high capacity can be obtained even when activated carbon as an active material is thinly applied. .
- the present invention is not limited to the foamed resin molded body, and an aluminum structure having an arbitrary shape can be obtained by using the resin molded body having an arbitrary shape. Can be obtained.
- Example Production of porous aluminum body: formation of aluminum layer by vapor deposition
- a production example of the aluminum porous body will be specifically described.
- a foamed resin molded body a urethane foam having a thickness of 1.6 mm, a porosity of 95%, and a number of pores (number of cells) per inch of about 50 was prepared and cut into 140 mm ⁇ 340 mm squares.
- Aluminum was deposited on the surface of the urethane foam to form a conductive layer having a thickness of about 1 ⁇ m.
- a noble metal layer having a thickness of 0.005 ⁇ m was formed by vapor-depositing gold on the resin molded body on which the conductive layer was formed.
- the means for evaporating gold was a method of irradiating an electron beam with an electron gun.
- An inert gas was introduced at a pressure of 0.01 to 1 Pa around the urethane with the conductive layer, and gold was melted by an electron beam to deposit a gold thin film on the surface of the conductive layer.
- a jig having a urethane foam having a conductive layer and a noble metal layer formed on the surface was connected to the cathode side of the rectifier, and a counter aluminum plate (purity 99.99%) was connected to the anode side.
- the jig can feed power from four sides of the urethane foam and can be plated in an area of 100 mm ⁇ 300 mm. It was immersed in a molten salt aluminum plating bath (67 mol% AlCl 3 -33 mol% EMIC) at a temperature of 40 ° C., and a direct current with a current density of 3.6 A / dm 2 was applied for 90 minutes to plate aluminum.
- the obtained porous aluminum body was dissolved in aqua regia and measured with an ICP (inductively coupled plasma) emission spectrometer.
- the carbon content was measured by a high frequency induction furnace combustion-infrared absorption method of JIS-G1211.
- the aluminum purity was 99% by mass and contained 0.5% by mass of carbon and 0.03% by mass of gold.
- EDX analysis of the surface at an acceleration voltage of 15 kV almost no oxygen peak was observed, and it was confirmed that the oxygen content of the aluminum porous body was below the EDX detection limit (3.1 mass%).
- a paste was prepared. The paste is filled in a porous aluminum body having a three-dimensional network structure and having a porosity of about 95%, and then vacuum-dried at 150 ° C., and further roll-pressed until the thickness reaches 70% of the initial thickness. (Positive electrode) was produced. This battery electrode material was punched out to 10 mm ⁇ , and fixed to a SUS304 coin battery container by spot welding. The positive electrode filling capacity was 2.4 mAh.
- LiCoO 2 , carbon black, and PVdF mixed paste were applied onto an aluminum foil having a thickness of 20 ⁇ m, and dried and roll-pressed in the same manner as described above to produce a battery electrode material (positive electrode).
- This battery electrode material was punched out to 10 mm ⁇ , and fixed to a SUS304 coin battery container by spot welding.
- the positive electrode filling capacity was 0.24 mAh.
- a polypropylene porous membrane having a thickness of 25 ⁇ m was used as a separator, and an EC / DEC (volume ratio 1: 1) solution in which 1M concentration of LiPF 6 was dissolved was added dropwise at 0.1 ml / cm 2 to the separator, and vacuum was applied. Impregnated.
- a lithium aluminum foil having a thickness of 20 ⁇ m and 11 mm ⁇ was used as the negative electrode, and was bonded and fixed to the upper cover of the coin battery container.
- the battery electrode material (positive electrode), separator, and negative electrode were laminated in this order, and a Viton O-ring was sandwiched between the upper lid and the lower lid to produce a battery.
- the upper limit voltage during heavy discharge was 4.2 V
- the lower limit voltage was 3.0 V
- discharging was performed at each discharge rate.
- the lithium secondary battery using the aluminum porous body as the positive electrode material had a capacity of about 5 times at a rate of 0.2 C compared with a conventional lithium foil battery electrode material. Further, a life cycle test was performed based on the cycle life described in JIS C 8711.
- the upper limit voltage at the time of charging / discharging was 4.2V
- the lower limit voltage was 3.0V
- after charging to the positive electrode filling capacity, the cycle of discharging at a discharge rate of 0.2C was repeated.
- the lithium secondary battery using an aluminum porous body as a positive electrode material has no particular decrease in voltage or capacity, and no problem in cycle characteristics is found, compared with a conventional lithium foil using an aluminum foil as an electrode material.
- a method for producing an aluminum structure comprising a plating step of plating aluminum in a first molten salt bath, While the resin molded body on which the aluminum plating layer is formed is immersed in the second molten salt, the resin molded body is decomposed by heating to a temperature below the melting point of aluminum while applying a negative potential to the aluminum plating layer.
- the manufacturing method of the aluminum structure which has a process to do.
- a method for producing an aluminum structure comprising a plating step of plating in a salt bath, and a dissolution step of dissolving the conductive layer after the plating step, Furthermore, a step of decomposing the resin molded body by heating to a temperature below the melting point of aluminum while applying a negative potential to the aluminum plated layer in a state where the resin molded body on which the aluminum plated layer is formed is immersed in a molten salt.
- a conductive step of forming a conductive layer made of aluminum on the surface of the resin molded body, a step of performing zinc substitution plating on the surface of the conductive layer to form a zinc film, and a resin molded body on which the zinc film is formed A plating process in which aluminum is plated in a first molten salt bath, and a resin molded body on which the aluminum plating layer is formed is immersed in the second molten salt while applying a negative potential to the aluminum plating layer.
- the manufacturing method of the aluminum structure which heats to the temperature below melting
- a method for producing an aluminum structure wherein the resin molded body is decomposed by heating to a temperature below the melting point of aluminum while applying a negative potential to the aluminum plating layer.
- (Appendix 5) The method for producing a porous aluminum body according to any one of appendices 1 to 4, wherein the resin molded body is a foamed resin molded body having continuous pores.
- (Appendix 6) The method for producing an aluminum structure according to appendix 2, wherein the molten salt bath used in the plating step is an imidazolium salt bath.
- (Appendix 7) The method for producing an aluminum structure according to appendix 2 or 6, wherein the molten salt bath is an imidazolium salt bath to which an organic solvent is added.
- (Appendix 8) The method for producing an aluminum structure according to appendix 7, wherein the addition of the organic solvent is 25 to 57 mol% of the entire plating bath.
- (Appendix 13) A battery using the electrode material according to appendix 12 for one or both of a positive electrode and a negative electrode.
- (Appendix 14) An electric double layer capacitor using the electrode material according to appendix 12 as an electrode.
- (Appendix 15) The filtration filter which consists of an aluminum structure obtained by this invention.
- (Appendix 16) A catalyst carrier having a catalyst supported on the surface of an aluminum structure obtained by the present invention.
- the present invention it is possible to obtain a structure in which the surface of a resin molded body is plated with aluminum, and an aluminum structure from which the resin molded body is removed.
- the present invention can be widely applied to the case where the characteristics of aluminum are utilized in electric materials, filters for various types of filtration, catalyst carriers, and the like.
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Abstract
Description
また、上記の製造方法において導電層を除去する場合に得られるアルミニウム構造体は、金属層として1μm~100μmの厚さのアルミニウム層を有するアルミニウム構造体であって、該金属層は、アルミニウムが98.0質量%以上、ニッケル、銅、コバルトおよび鉄の合計量が0.0001質量%以上2質量%未満、残部不可避不純物からなるアルミニウム構造体である(本願第16の発明)。
図1は、本発明による第1の実施の形態のアルミニウム構造体の製造工程を示すフロー図である。また図2は、フロー図に対応して樹脂成形体を芯材としてアルミニウム構造体を形成する様子を模式的に示したものである。両図を参照して製造工程全体の流れを説明する。まず基体樹脂成形体の準備101を行う。図2(a)は、基体樹脂成形体の例として、連通気孔を有する発泡樹脂成形体の表面を拡大視した樹脂の断面の一部を示す拡大模式図である。発泡樹脂成形体1を骨格として気孔が形成されている。次に樹脂成形体表面の導電化102を行う。この工程により、図2(b)に示すように樹脂成形体1の表面には、薄く導電層2が形成される。続いて溶融塩中でのアルミニウムめっき103を行い、導電層が形成された樹脂成形体の表面にアルミニウムめっき層3を形成する(図2(c))。これで、基体樹脂成形体を基材として表面にアルミニウムめっき層3が形成されたアルミニウム構造体が得られる。さらに、基体樹脂成形体の除去104を行っても良い。発泡樹脂成形体1を分解等して消失させることにより金属層のみが残ったアルミニウム構造体(多孔体)を得ることができる(図2(d))。
以下各工程について順を追って説明する。
三次元網目構造を有し連通気孔を有する多孔質樹脂成形体を準備する。多孔質樹脂成形体の素材は、任意の樹脂を選択できる。ポリウレタン、メラミン、ポリプロピレン、ポリエチレン等の発泡樹脂成形体が素材として例示できる。発泡樹脂成形体と表記したが、連続した気孔(連通気孔)を有するものであれば任意の形状の樹脂成形体を選択できる。例えば繊維状の樹脂を絡めて不織布のような形状を有するものも発泡樹脂成形体に代えて使用可能である。発泡樹脂成形体の気孔率は、80%~98%、気孔径は、50μm~500μmとするのが好ましい。発泡ウレタン及び発泡メラミンは、気孔率が高く、また気孔の連通性があるとともに熱分解性にも優れているため発泡樹脂成形体として好ましく使用できる。発泡ウレタンは、気孔の均一性や入手の容易さ等の点で好ましく、発泡ウレタンは、気孔径の小さなものが得られる点で好ましい。
気孔率=(1-(多孔質材の重量[g]/(多孔質材の体積[cm3]×素材密度)))×100[%]
また、気孔径は、樹脂成形体表面を顕微鏡写真等で拡大し、1インチ(25.4mm)あたりのセル数を計数して、平均孔径=25.4mm/セル数として平均的な値を求める。なお、以下の他の実施の形態においても、同様に気孔率、平均孔径を測定する。
まず発泡樹脂成形体の表面に金、銀、白金、ロジウム、ルテニウム及びパラジウムからなる群より選択される1種以上の貴金属からなる導電層を形成する。導電層の形成は、無電解めっきの他、スパッタ、プラズマCVD等の気相法、塗料の塗布等任意の方法で行うことができる。薄い膜を均一に形成するには、蒸着法などの気相法が好ましく適用できる。導電層の厚みは、0.001μm~0.2μm、好ましくは、0.01μm~0.1μmとすることが好ましい。導電層の厚みが0.001μmよりも薄い場合は、導電化が不十分であり、次の工程で良好に電解めっきを行うことができない。また厚みが0.2μmを超えると導電化工程のコストが高くなる。発泡樹脂成形体では、厚さが厚くなると深部まで全体に均一な層を形成するために無電解めっきなども用いることができる。
次に溶融塩中で電解めっきを行い、樹脂成形体表面にアルミニウムめっき層3を形成する。表面が導電化された樹脂成形体を陰極、純度99.99%のアルミニウム板を陽極として溶融塩中で直流電流を印加する。アルミニウムめっき層の厚みは、1μm~100μm、好ましくは、5μm~20μmである。溶融塩としては、有機系ハロゲン化物とアルミニウムハロゲン化物の共晶塩である有機溶融塩、アルカリ金属のハロゲン化物とアルミニウムハロゲン化物の共晶塩である無機溶融塩を使用することができる。比較的低温で溶融する有機溶融塩浴を使用すると、基材である樹脂成形体を分解することなくめっきができ好ましい。有機系ハロゲン化物としては、イミダゾリウム塩、ピリジニウム塩等が使用できる。なかでも1-エチル-3-メチルイミダゾリウムクロライド(EMIC)、ブチルピリジニウムクロライド(BPC)が好ましい。イミダゾリウム塩として、1,3位にアルキル基を持つイミダゾリウムカチオンを含む塩が好ましく用いられ、特に塩化アルミニウム、1-エチル-3-メチルイミダゾリウムクロライド(AlCl3-EMIC)系溶融塩が、安定性が高く分解し難いことから最も好ましく用いられる。
以上の工程により骨格の芯として樹脂成形体を有するアルミニウム構造体(アルミニウム多孔体)が得られる。各種フィルタや触媒担体などの用途によっては、このまま樹脂と金属の複合体として使用しても良い。また使用環境の制約などから、樹脂が無い金属構造体として用いる場合には、樹脂を除去しても良い。樹脂の除去は、有機溶媒、溶融塩、又は超臨界水による分解(溶解)、加熱分解等任意の方法で行うことができる。ここで、高温での加熱分解等の方法は、簡便であるが、アルミニウムの酸化を伴う。アルミニウムは、ニッケル等と異なり、一旦酸化すると還元処理が困難であるため、たとえば電池等の電極材料として使用する場合には、酸化により導電性が失われることから用いることが出来ない。このため、アルミニウムの酸化が起こらないように、以下に説明する溶融塩中での熱分解により樹脂を除去する方法が好ましく用いられる。
次にアルミニウム多孔体を用いた電池用電極材料及び電池について説明する。例えばリチウムイオン電池の正極に使用する場合は、活物質としてコバルト酸リチウム(LiCoO2)、マンガン酸リチウム(LiMn2O4)、ニッケル酸リチウム(LiNiO2)等を使用する。活物質は、導電助剤及びバインダーと組み合わせて使用する。従来のリチウムイオン電池用正極材料は、アルミニウム箔の表面に活物質を塗布している。単位面積当たりの電池容量を向上するために、活物質の塗布厚みを厚くしている。また活物質を有効に利用するためには、アルミニウム箔と活物質とが電気的に接触している必要があるので活物質は、導電助剤と混合して用いられている。これに対し、本発明のアルミニウム多孔体は、気孔率が高く単位面積当たりの表面積が大きい。よって多孔体の表面に薄く活物質を担持させても活物質を有効に利用でき、電池の容量を向上できるとともに、導電助剤の混合量を少なくすることができる。リチウムイオン電池は、上記の正極材料を正極とし、負極には黒鉛、電解質には有機電解液を使用する。このようなリチウムイオン電池は、小さい電極面積でも容量を向上できるため、従来のリチウムイオン電池よりも電池のエネルギー密度を高くすることができる。また、本願発明のアルミニウム多孔体においては、アルミニウム以外に導電層として形成した金属材料が残留するが、これら金属は、電池の充放電サイクルにおいて溶出することが無く問題とならない。
アルミニウム多孔体は、溶融塩電池用の電極材料として使用することもできる。アルミニウム多孔体を正極材料として使用する場合は、活物質としてクロム酸ナトリウム(NaCrO2)、二硫化チタン(TiO2)等、電解質となる溶融塩のカチオンをインターカレーションすることができる金属化合物を使用する。活物質は、導電助剤及びバインダーと組み合わせて使用する。導電助剤としては、アセチレンブラック等が使用できる。またバインダーとしては、ポリテトラフルオロエチレン(PTFE)等を使用できる。活物質としてクロム酸ナトリウムを使用し、導電助剤としてアセチレンブラックを使用する場合には、PTFEは、この両者をより強固に固着することができ好ましい。
アルミニウム多孔体は、電気二重層コンデンサ用の電極材料として使用することもできる。アルミニウム多孔体を電気二重層コンデンサ用の電極材料として使用する場合は、電極活物質として活性炭等を使用する。活性炭は、導電助剤やバインダーと組み合わせて使用する。導電助剤としては、黒鉛、カーボンナノチューブ等が使用できる。またバインダーとしては、ポリテトラフルオロエチレン(PTFE)、スチレンブタジエンゴム等を使用できる。
以下、アルミニウム多孔体の製造例を具体的に説明する。発泡樹脂成形体として、厚み1.6mm、気孔率95%、1cm当たりの気孔数約20個のウレタン発泡体を準備し、140mm×340mmに切断した。
ウレタン発泡体の表面に蒸着法によって金を蒸着することで0.02μm厚の導電層を形成した。金を蒸発させる手段は、電子銃により電子ビームを照射する方法とした。ウレタンの周囲に不活性ガスを圧力は、0.01~1Paの範囲で導入し、電子ビームにより金を溶融して、ウレタン上に金薄膜を蒸着した。
表面に導電層を形成したウレタン発泡体を給電機能を有する治具にセットした。治具は、ウレタン発泡体の4辺からの給電が可能で100mm×300mmのエリアにめっき可能としたものである。セットしたウレタン発泡体を、アルゴン雰囲気かつ低水分(露点-30℃以下)としたグローブボックス内に入れ、温度40℃の溶融塩アルミめっき浴(67mol%AlCl3-33mol%EMIC)に浸漬した。ウレタン発泡体をセットした治具を整流器の陰極側に接続し、対極のアルミニウム板(純度99.99%)を陽極側に接続した。治具は、ウレタン発泡体の4辺からの給電が可能なように4辺に電極を設けたものである。電流密度3.6A/dm2の直流電流を60分間印加してアルミニウムをめっきした。攪拌は、テフロン(登録商標)製の回転子を用いてスターラーにて行った。なお電流密度の計算では、アルミニウム多孔体の見かけの面積を使用している(ウレタン発泡体の実表面積は、見かけの面積の約8倍)。この結果、120g/m2の重量のアルミめっき皮膜をほぼ均一に形成することができた。
アルミニウムめっき層を形成した発泡樹脂を温度500℃のLiCl-KCl共晶溶融塩に浸漬し、-1Vの負電位を30分間印加した。溶融塩中に気泡が発生し、ポリウレタンの分解反応が起こっていると推定された。その後大気中で室温まで冷却した後、水洗して溶融塩を除去しアルミニウム多孔体を得た。
アルミニウム多孔体の実用上の評価例として電池用電極に用いた場合をアルミニウム箔を電極とした従来構造との比較で説明する。
図8は、本発明による第2の実施の形態のアルミニウム構造体の製造工程を示すフロー図である。また、図2に示すように、本発明による第1の実施の形態と同様に基体樹脂成形体を基材として表面にアルミニウムめっき層3が形成されたアルミニウム構造体が得られる。さらに、基体樹脂成形体の除去104を行っても良い。また、用途によって導電層の除去105を行うと良い。発泡樹脂成形体1を分解等して消失させることにより金属層のみが残ったアルミニウム構造体(多孔体)を得ることができる。
以下各工程について順を追って説明する。
三次元網目構造を有し連通気孔を有する多孔質樹脂成形体は、本発明による第1の実施の形態と同様に準備する。多孔質樹脂成形体の素材は、任意の樹脂を選択できる。ポリウレタン、メラミン、ポリプロピレン、ポリエチレン等の発泡樹脂成形体が素材として例示できる。
まず発泡樹脂成形体の表面にニッケル、銅、コバルト、及び鉄からなる群より選択される1種以上の金属からなる導電層を形成する。導電層の形成は、無電解めっきの他、蒸着、スパッタ、プラズマCVD等の気相法、塗料の塗布等任意の方法で行うことができる。薄い膜を形成するには、蒸着法などの気相法も好ましく適用できるが、発泡樹脂成形体では、厚さが厚くなると深部まで全体に均一な層を形成するために無電解めっきが好ましい。導電層の厚みは、0.01μm~1μm、好ましくは、0.1μm~0.5μmとすることが好ましい。導電層の厚みが0.01μmよりも薄い場合は、導電化が不十分であり、次の工程で良好に電解めっきを行うことができない。また厚みが1μmを超えると導電化工程のコストが高くなる。
次に溶融塩中で電解めっきを行い、樹脂成形体表面にアルミニウムめっき層3を形成する。表面が導電化された樹脂成形体を陰極、純度99.99%のアルミニウム板を陽極として溶融塩中で直流電流を印加する。アルミニウムめっき層の厚みは、1μm~100μm、好ましくは、5μm~20μmである。溶融塩としては、有機系ハロゲン化物とアルミニウムハロゲン化物の共晶塩である有機溶融塩、アルカリ金属のハロゲン化物とアルミニウムハロゲン化物の共晶塩である無機溶融塩を使用することができる。比較的低温で溶融する有機溶融塩浴を使用すると、基材である樹脂成形体を分解することなくめっきができ好ましい。有機系ハロゲン化物としては、イミダゾリウム塩、ピリジニウム塩等が使用できる。なかでも1-エチル-3-メチルイミダゾリウムクロライド(EMIC)、ブチルピリジニウムクロライド(BPC)が好ましい。イミダゾリウム塩として、1,3位にアルキル基を持つイミダゾリウムカチオンを含む塩が好ましく用いられ、特に塩化アルミニウム、1-エチル-3-メチルイミダゾリウムクロライド(AlCl3-EMIC)系溶融塩が、安定性が高く分解し難いことから最も好ましく用いられる。
以上の工程により骨格の芯として樹脂成形体を有するアルミニウム構造体(アルミニウム多孔体)が得られる。各種フィルタや触媒担体などの用途によっては、このまま樹脂と金属の複合体として使用しても良い。また使用環境の制約などから、樹脂が無い金属構造体として用いる場合には、樹脂を除去しても良い。樹脂の除去は、有機溶媒、溶融塩、又は超臨界水による分解(溶解)、加熱分解等任意の方法で行うことができる。ここで、高温での加熱分解等の方法は、簡便であるが、アルミニウムの酸化を伴う。アルミニウムは、ニッケル等と異なり、一旦酸化すると還元処理が困難であるため、たとえば電池等の電極材料として使用する場合には、酸化により導電性が失われることから用いることが出来ない。このため、アルミニウムの酸化が起こらないように、以下に説明する溶融塩中での熱分解により樹脂を除去する方法が好ましく用いられる。
導電層の溶解は、酸、特に酸化性の酸である濃硝酸に浸漬することによりアルミニウムを溶解させることなく導電層を除去することで行う。アルミニウムは、表面に酸化性の酸の中で不働態皮膜を形成するために酸の中でも溶解せず、一方、導電層に使用した金属は、溶解する。例えばニッケルを導電層とする場合、15℃~35℃の濃硝酸67.5%中に1~30分浸漬後、水洗、乾燥するとよい。他の金属を導電層とする場合においてもそれぞれ溶解する酸を選択して使用できればよい。
次にアルミニウム多孔体を用いた電池用電極材料及び電池について説明する。例えばリチウムイオン電池の正極に使用する場合は、活物質としてコバルト酸リチウム(LiCoO2)、マンガン酸リチウム(LiMn2O4)、ニッケル酸リチウム(LiNiO2)等を使用する。活物質は、導電助剤及びバインダーと組み合わせて使用する。従来のリチウムイオン電池用正極材料は、アルミニウム箔の表面に活物質を塗布している。単位面積当たりの電池容量を向上するために、活物質の塗布厚みを厚くしている。また活物質を有効に利用するためには、アルミニウム箔と活物質とが電気的に接触している必要があるので活物質は、導電助剤と混合して用いられている。これに対し、本発明のアルミニウム多孔体は、気孔率が高く単位面積当たりの表面積が大きい。よって多孔体の表面に薄く活物質を担持させても活物質を有効に利用でき、電池の容量を向上できるとともに、導電助剤の混合量を少なくすることができる。リチウムイオン電池は、上記の正極材料を正極とし、負極には、黒鉛、電解質には、有機電解液を使用する。このようなリチウムイオン電池は、小さい電極面積でも容量を向上できるため、従来のリチウムイオン電池よりも電池のエネルギー密度を高くすることができる。
アルミニウム多孔体は、溶融塩電池用の電極材料として使用することもできる。アルミニウム多孔体を正極材料として使用する場合は、活物質としてクロム酸ナトリウム(NaCrO2)、二硫化チタン(TiO2)等、電解質となる溶融塩のカチオンをインターカレーションすることができる金属化合物を使用する。活物質は、導電助剤及びバインダーと組み合わせて使用する。導電助剤としては、アセチレンブラック等が使用できる。またバインダーとしては、ポリテトラフルオロエチレン(PTFE)等を使用できる。活物質としてクロム酸ナトリウムを使用し、導電助剤としてアセチレンブラックを使用する場合には、PTFEは、この両者をより強固に固着することができ好ましい。
アルミニウム多孔体は、電気二重層コンデンサ用の電極材料として使用することもできる。アルミニウム多孔体を電気二重層コンデンサ用の電極材料として使用する場合は、電極活物質として活性炭等を使用する。活性炭は、導電助剤やバインダーと組み合わせて使用する。導電助剤としては、黒鉛、カーボンナノチューブ等が使用できる。またバインダーとしては、ポリテトラフルオロエチレン(PTFE)、スチレンブタジエンゴム等を使用できる。
以下、アルミニウム多孔体の製造例を具体的に説明する。発泡樹脂成形体として、厚み1mm、気孔率95%、1インチ当たりの気孔数(セル数)約50個のウレタン発泡体を準備し、140mm×340mに切断した。
ウレタン発泡体の表面に無電解ニッケルめっきを行い、導電層を形成した。処理工程は、以下の通りである。
・親水化処理;アルカリ+カチオン系界面活性剤+ノニオン系界面活性剤、50℃、2分
・水洗
・酸処理;8%塩酸、室温、30秒
・触媒付け;塩酸+キャタリストC(奥野製薬)、20℃、3分
・水洗
・活性化;硫酸+アクセレータX(奥野製薬)45℃、2分
・水洗
・無電解めっき;めっき液(硫酸Ni:22g/L、次亜リン酸Na:20g/L、クエン酸Na:40g/L、ホウ酸アンモニウム:10g/L、安定剤:1ppm)をアンモニア水にてpH=9に調整、35℃、3分
・水洗
・乾燥
こうして得られた無電解Niめっきの目付量は、10g/m2で組成は、Ni-3wt%Pであった。
表面に導電層を形成したウレタン発泡体を、給電機能を有する治具にセットした後、温度40℃の溶融塩アルミめっき浴(17mol%EMIC-34mol%AlCl3-49mol%キシレン)に浸漬した。ウレタン発泡体をセットした治具を整流器の陰極側に接続し、対極のアルミニウム板(純度99.99%)を陽極側に接続した。電流密度3.6A/dm2の直流電流を60分間印加してアルミニウムをめっきした。攪拌は、テフロン(登録商標)製の回転子を用いてスターラーにて行った。なお電流密度の計算では、アルミニウム多孔体の見かけの面積を使用している(ウレタン発泡体の実表面積は、見かけの面積の約8倍)。この結果、120g/m2の重量のアルミめっき皮膜をほぼ均一に形成することができた。
めっき浴として温度40℃の溶融塩アルミめっき浴(33mol%EMIC-67mol%AlCl3)を用いた他は、上記と同様にめっきを行い同じく目付量120g/m2のアルミニウム多孔体を得た。
アルミニウムめっき層を形成した発泡樹脂を温度500℃のLiCl-KCl共晶溶融塩に浸漬し、-1Vの負電位を30分間印加した。溶融塩中に気泡が発生し、ポリウレタンの分解反応が起こっていると推定された。その後大気中で室温まで冷却した後、水洗して溶融塩を除去しアルミニウム多孔体を得た。
得られたアルミニウム多孔体を、室温の67.5%濃硝酸中に5分浸漬後、水洗、乾燥して導電層としてのニッケルを溶解させた。濃硝酸によりニッケルは、溶解するが、アルミニウムは、表面に酸化性の酸の中で不働態皮膜を形成するために、酸の中でも溶解しない。これによりニッケルがほぼ除去され、アルミニウム純度の高いアルミニウム多孔体を得ることができる。
アルミニウム多孔体の実用上の評価例として電池用電極に用いた場合を、アルミニウム箔を電極とした従来構造との比較で説明する。
図13は、本発明による第3の実施の形態のアルミニウム構造体の製造工程を示すフロー図である。また、図2に示すように、本発明による第1の実施の形態と同様に基体樹脂成形体を基材として表面にアルミニウムめっき層3が形成されたアルミニウム構造体が得られる。なお、図2(b)に示すように樹脂成形体1の表面には、薄くアルミニウムからなる導電層2が形成される。さらに、導電層2表面に亜鉛置換めっきにより亜鉛皮膜を形成する工程103を行う。亜鉛皮膜は、ごく薄く付着されるため、図2には、図示していない。続いて溶融塩中でのアルミニウムめっき104を行い、導電層が形成された樹脂成形体の表面にアルミニウムめっき層3を形成する(図2(c))。これで、基体樹脂成形体を基材として表面にアルミニウムめっき層3が形成されたアルミニウム構造体が得られる。さらに、基体樹脂成形体の除去105を行っても良い。発泡樹脂成形体1を分解等して消失させることにより金属層のみが残ったアルミニウム構造体(多孔体)を得ることができる(図2(d))。
以下各工程について順を追って説明する。
三次元網目構造を有し連通気孔を有する多孔質樹脂成形体は、本発明による第1の実施の形態と同様に準備する。多孔質樹脂成形体の素材は、任意の樹脂を選択できる。ポリウレタン、メラミン、ポリプロピレン、ポリエチレン等の発泡樹脂成形体が素材として例示できる。
まず発泡樹脂成形体の表面にアルミニウムからなる導電層を形成する。導電層の形成は、蒸着、スパッタ、プラズマCVD等の気相法、アルミニウム塗料の塗布等任意の方法で行うことができる。薄い膜を均一に形成できるため、蒸着法が好ましい。導電層の厚みは、0.05μm~5μm、好ましくは、0.1μm~3μmとする。導電層の厚みが0.05μmよりも薄い場合は、導電化が不十分であり、次の工程で良好に電解めっきを行うことができない。また導電層の厚みが薄すぎると亜鉛置換めっき工程において良好に亜鉛皮膜を形成できない。厚みが5μmを超えると導電化工程のコストが高くなる。
導電化処理は、発泡樹脂成形体を、アルミニウムを含む塗料に浸漬して行っても良い。塗料に含まれているアルミニウム成分が発泡樹脂成形体の表面に付着してアルミニウムからなる導電層が形成されることで、溶融塩中でめっき可能な導電状態となる。アルミニウムを含む塗料としては、例えば粒径10nm~1μmのアルミニウム微粒子を水または有機溶剤中に分散させた液を使用できる。発泡樹脂を塗料に浸漬した後加熱して溶剤を蒸発させることで導電層を形成できる。
上記工程で形成された導電層の上に、溶融塩めっきによりアルミニウムをめっきしてアルミニウムめっき層を形成する。このとき導電層の表面に酸化膜が存在すると、次のめっき工程においてアルミニウムの付着性が悪くなり、島状にアルミニウムが付着したり、アルミニウムめっき層の厚みにばらつきが生じる可能性がある。そこでめっき工程の前に亜鉛置換めっきを行い導電層の表面に亜鉛皮膜を形成する。亜鉛置換めっきは、以下のように行う。
次に溶融塩中で電解めっきを行い、樹脂成形体表面にアルミニウムめっき層3を形成する。表面が導電化された樹脂成形体を陰極、純度99.99%のアルミニウム板を陽極として溶融塩中で直流電流を印加する。アルミニウムめっき層の厚みは、1μm~100μm、好ましくは、5μm~20μmである。陽極電解処理とは、逆に導電化された樹脂成形体を陰極、対極を陽極として溶融塩中で直流電流を印加する。溶融塩としては、有機系ハロゲン化物とアルミニウムハロゲン化物の共晶塩である有機溶融塩、アルカリ金属のハロゲン化物とアルミニウムハロゲン化物の共晶塩である無機溶融塩を使用することができる。比較的低温で溶融する有機溶融塩浴を使用すると、基材である樹脂成形体を分解することなくめっきができ好ましい。有機系ハロゲン化物としては、イミダゾリウム塩、ピリジニウム塩等が使用できる。なかでも1-エチル-3-メチルイミダゾリウムクロライド(EMIC)、ブチルピリジニウムクロライド(BPC)が好ましい。イミダゾリウム塩として、1,3位にアルキル基を持つイミダゾリウムカチオンを含む塩が好ましく用いられ、特に塩化アルミニウム、1-エチル-3-メチルイミダゾリウムクロライド(AlCl3-EMIC)系溶融塩が、安定性が高く分解し難いことから最も好ましく用いられる。
溶融塩中での熱分解は、以下の方法で行う。表面にアルミニウムめっき層を形成した、アルミニウムめっき層付き発泡樹脂成形体を溶融塩に浸漬し、該アルミニウム層に負電位を印加しながら加熱して発泡樹脂成形体を分解する。溶融塩に浸漬した状態で負電位を印加するとアルミニウムの酸化反応を防止できる。このような状態で加熱することでアルミニウムを酸化させることなく発泡樹脂成形体を分解することができる。加熱温度は、発泡樹脂成形体の種類に合わせて適宜選択できるが、アルミニウムを溶融させないためには、アルミニウムの融点(660℃)以下の温度で処理する必要がある。好ましい温度範囲は、500℃以上600℃以下である。また印加する負電位の量は、アルミニウムの還元電位よりマイナス側で、かつ溶融塩中のカチオンの還元電位よりプラス側とする。
次にアルミニウム多孔体を用いた電池用電極材料及び電池について説明する。例えばリチウムイオン電池の正極に使用する場合は、活物質としてコバルト酸リチウム(LiCoO2)、マンガン酸リチウム(LiMn2O4)、ニッケル酸リチウム(LiNiO2)等を使用する。活物質は、導電助剤及びバインダーと組み合わせて使用する。従来のリチウムイオン電池用正極材料は、アルミニウム箔の表面に活物質を塗布している。単位面積当たりの電池容量を向上するために、活物質の塗布厚みを厚くしている。また活物質を有効に利用するためには、アルミニウム箔と活物質とが電気的に接触している必要があるので活物質は、導電助剤と混合して用いられている。これに対し、本発明のアルミニウム多孔体は、気孔率が高く単位面積当たりの表面積が大きい。よって多孔体の表面に薄く活物質を担持させても活物質を有効に利用でき、電池の容量を向上できるとともに、導電助剤の混合量を少なくすることができる。リチウムイオン電池は、上記の正極材料を正極とし、負極には、黒鉛、電解質には、有機電解液を使用する。このようなリチウムイオン電池は、小さい電極面積でも容量を向上できるため、従来のリチウムイオン電池よりも電池のエネルギー密度を高くすることができる。
アルミニウム多孔体は、溶融塩電池用の電極材料として使用することもできる。アルミニウム多孔体を正極材料として使用する場合は、活物質としてクロム酸ナトリウム(NaCrO2)、二硫化チタン(TiO2)等、電解質となる溶融塩のカチオンをインターカレーションすることができる金属化合物を使用する。活物質は、導電助剤及びバインダーと組み合わせて使用する。導電助剤としては、アセチレンブラック等が使用できる。またバインダーとしては、ポリテトラフルオロエチレン(PTFE)等を使用できる。活物質としてクロム酸ナトリウムを使用し、導電助剤としてアセチレンブラックを使用する場合には、PTFEは、この両者をより強固に固着することができ好ましい。
アルミニウム多孔体は、電気二重層コンデンサ用の電極材料として使用することもできる。アルミニウム多孔体を電気二重層コンデンサ用の電極材料として使用する場合は、電極活物質として活性炭等を使用する。活性炭は、導電助剤やバインダーと組み合わせて使用する。導電助剤としては、黒鉛、カーボンナノチューブ等が使用できる。またバインダーとしては、ポリテトラフルオロエチレン(PTFE)、スチレンブタジエンゴム等を使用できる。
以下、アルミニウム多孔体の製造例を具体的に説明する。発泡樹脂成形体として、厚み1.6mm、気孔率95%、1cm当たりの気孔数約20個のウレタン発泡体を準備し、140mm×190mm角に切断した。ウレタン発泡体の表面にアルミニウムを蒸着し、厚み約2.5μmの導電層を形成した。
導電層を形成した樹脂成形体を、10℃に温度制御した亜鉛置換めっき処理液(奥野製薬(株)製、サブスターZN)に15秒間浸漬し、亜鉛置換めっきを行った。その後水洗し、乾燥して亜鉛皮膜が形成された樹脂組成物を得た。
ウレタン発泡体をセットした治具を整流器の陰極側に接続し、対極のアルミニウム板(純度99.99%)を陽極側に接続した。治具は、ウレタン発泡体の4辺からの給電が可能で100mm×150mmのエリアにめっき可能としたものである。温度40℃の溶融塩アルミめっき浴(67mol%AlCl3-33mol%EMIC)に浸漬し、電流密度3.6A/dm2の直流電流を60分間印加してアルミニウムをめっきした。攪拌は、テフロン(登録商標)製の回転子を用いてスターラーにて行った。なお一連の操作は、アルゴン雰囲気かつ低水分(露点-30℃以下)としたグローブボックス内で行った。また電流密度の計算では、アルミニウム多孔体の見かけの面積を使用している(ウレタン発泡体の実表面積は、見かけの面積の約8倍)。この結果、120g/m2の重量のアルミニウムめっき皮膜をほぼ均一に形成することができた。
アルミニウムめっき層を形成した発泡樹脂を温度500℃のLiCl-KCl共晶溶融塩に浸漬し、-1Vの負電位を30分間印加した。溶融塩中に気泡が発生し、ポリウレタンの分解反応が起こっていると推定された。その後大気中で室温まで冷却した後、水洗して溶融塩を除去しアルミニウム多孔体を得た。得られたアルミニウム多孔体のSEM写真を図14に示す。
アルミニウム多孔体の実用上の評価例として電池用電極に用いた場合を、アルミニウム箔を電極とした従来構造との比較で説明する。
図15は、本発明による本発明による第4の実施の形態のアルミニウム構造体の製造工程を示すフロー図である。また図2は、フロー図に対応して樹脂成形体を芯材としてアルミニウム構造体を形成する様子を模式的に示したものである。なお、図2(b)に示すように樹脂成形体1の表面には、薄くアルミニウムからなる導電層2が形成される。さらに、導電層2の表面に貴金属を付着する工程103を行う。貴金属は、ごく薄く付着されるため、図2には、図示していない。続いて溶融塩中でのアルミニウムめっき104を行い、導電層が形成された樹脂成形体の表面にアルミニウムめっき層3を形成する(図2(c))。これで、基体樹脂成形体を基材として表面にアルミニウムめっき層3が形成されたアルミニウム構造体が得られる。さらに、基体樹脂成形体の除去105を行っても良い。発泡樹脂成形体1を分解等して消失させることにより金属層のみが残ったアルミニウム構造体(多孔体)を得ることができる(図2(d))。
以下各工程について順を追って説明する。
三次元網目構造を有し連通気孔を有する多孔質樹脂成形体は、本発明による第1の実施の形態と同様に準備する。多孔質樹脂成形体の素材は、任意の樹脂を選択できる。ポリウレタン、メラミン、ポリプロピレン、ポリエチレン等の発泡樹脂成形体が素材として例示できる。
まず発泡樹脂成形体の表面にアルミニウムからなる導電層を形成する。導電層の形成は、蒸着、スパッタ、プラズマCVD等の気相法、アルミニウム塗料の塗布等任意の方法で行うことができる。薄い膜を均一に形成できるため、蒸着法が好ましい。導電層の厚みは、0.05μm~1μm、好ましくは、0.1μm~0.5μmとすることが好ましい。導電層の厚みが0.01μmよりも薄い場合は、導電化が不十分であり、次の工程で良好に電解めっきを行うことができない。また厚みが1μmを超えると導電化工程のコストが高くなる。
導電化処理は、発泡樹脂成形体を、アルミニウムを含む塗料に浸漬して行っても良い。塗料に含まれているアルミニウム成分が発泡樹脂成形体の表面に付着してアルミニウムからなる導電層が形成されることで、溶融塩中でめっき可能な導電状態となる。アルミニウムを含む塗料としては、例えば粒径10nm~1μmのアルミニウム微粒子を水または有機溶剤中に分散させた液を使用できる。発泡樹脂を塗料に浸漬した後加熱して溶剤を蒸発させることで導電層を形成できる。
上記工程で形成された導電層の上に、溶融塩めっきによりアルミニウムをめっきしてアルミニウムめっき層を形成する。このとき導電層の表面に酸化膜が存在すると、次のめっき工程においてアルミニウムの付着性が悪くなり、島状にアルミニウムが付着したり、アルミニウムめっき層の厚みにばらつきが生じる可能性がある。そこでめっき工程の前に導電層(アルミニウム層)表面に貴金属を付着させる。貴金属の付着は、蒸着、スパッタ、プラズマCVD等の気相法、無電解めっき、貴金属を含む塗料の塗布等任意の方法で行うことができる。薄い膜を均一に形成できるため、蒸着法が好ましい。これらの貴金属は、非常に高価であるので、コストの点からは、薄い方が好ましい。貴金属層の厚みは、0.0001μm~1μm、好ましくは、0.001μm~0.01μmとする。貴金属層の厚みが0.0001μmよりも薄い場合は、アルミニウムの酸化膜を完全に被覆することができず、良好なめっきが行えない。貴金属層の厚みが1μmを超えると導電化工程のコストが高くなる。
次に溶融塩中で電解めっきを行い、樹脂成形体表面にアルミニウムめっき層3を形成する。表面が導電化された樹脂成形体を陰極、純度99.99%のアルミニウム板を陽極として溶融塩中で直流電流を印加する。アルミニウムめっき層の厚みは、1μm~100μm、好ましくは、5μm~20μmである。陽極電解処理とは逆に導電化された樹脂成形体を陰極、対極を陽極として溶融塩中で直流電流を印加する。溶融塩としては、有機系ハロゲン化物とアルミニウムハロゲン化物の共晶塩である有機溶融塩、アルカリ金属のハロゲン化物とアルミニウムハロゲン化物の共晶塩である無機溶融塩を使用することができる。比較的低温で溶融する有機溶融塩浴を使用すると、基材である樹脂成形体を分解することなくめっきができ好ましい。有機系ハロゲン化物としては、イミダゾリウム塩、ピリジニウム塩等が使用できる。なかでも1-エチル-3-メチルイミダゾリウムクロライド(EMIC)、ブチルピリジニウムクロライド(BPC)が好ましい。イミダゾリウム塩として、1,3位にアルキル基を持つイミダゾリウムカチオンを含む塩が好ましく用いられ、特に塩化アルミニウム、1-エチル-3-メチルイミダゾリウムクロライド(AlCl3-EMIC)系溶融塩が、安定性が高く分解し難いことから最も好ましく用いられる。
溶融塩中での熱分解は、以下の方法で行う。表面にアルミニウムめっき層を形成した、アルミニウムめっき層付き発泡樹脂成形体を溶融塩に浸漬し、該アルミニウム層に負電位を印加しながら加熱して発泡樹脂成形体を分解する。溶融塩に浸漬した状態で負電位を印加するとアルミニウムの酸化反応を防止できる。このような状態で加熱することでアルミニウムを酸化させることなく発泡樹脂成形体を分解することができる。加熱温度は、発泡樹脂成形体の種類に合わせて適宜選択できるが、アルミニウムを溶融させないためには、アルミニウムの融点(660℃)以下の温度で処理する必要がある。好ましい温度範囲は、500℃以上600℃以下である。また印加する負電位の量は、アルミニウムの還元電位よりマイナス側で、かつ溶融塩中のカチオンの還元電位よりプラス側とする。
次にアルミニウム多孔体を用いた電池用電極材料及び電池について説明する。例えばリチウムイオン電池の正極に使用する場合は、活物質としてコバルト酸リチウム(LiCoO2)、マンガン酸リチウム(LiMn2O4)、ニッケル酸リチウム(LiNiO2)等を使用する。活物質は、導電助剤及びバインダーと組み合わせて使用する。従来のリチウムイオン電池用正極材料は、アルミニウム箔の表面に活物質を塗布している。単位面積当たりの電池容量を向上するために、活物質の塗布厚みを厚くしている。また活物質を有効に利用するためには、アルミニウム箔と活物質とが電気的に接触している必要があるので活物質は、導電助剤と混合して用いられている。これに対し、本発明のアルミニウム多孔体は、気孔率が高く単位面積当たりの表面積が大きい。よって多孔体の表面に薄く活物質を担持させても活物質を有効に利用でき、電池の容量を向上できるとともに、導電助剤の混合量を少なくすることができる。リチウムイオン電池は、上記の正極材料を正極とし、負極には黒鉛、電解質には有機電解液を使用する。このようなリチウムイオン電池は、小さい電極面積でも容量を向上できるため、従来のリチウムイオン電池よりも電池のエネルギー密度を高くすることができる。
アルミニウム多孔体は、溶融塩電池用の電極材料として使用することもできる。アルミニウム多孔体を正極材料として使用する場合は、活物質としてクロム酸ナトリウム(NaCrO2)、二硫化チタン(TiO2)等、電解質となる溶融塩のカチオンをインターカレーションすることができる金属化合物を使用する。活物質は、導電助剤及びバインダーと組み合わせて使用する。導電助剤としては、アセチレンブラック等が使用できる。またバインダーとしては、ポリテトラフルオロエチレン(PTFE)等を使用できる。活物質としてクロム酸ナトリウムを使用し、導電助剤としてアセチレンブラックを使用する場合には、PTFEは、この両者をより強固に固着することができ好ましい。
アルミニウム多孔体は、電気二重層コンデンサ用の電極材料として使用することもできる。アルミニウム多孔体を電気二重層コンデンサ用の電極材料として使用する場合は、電極活物質として活性炭等を使用する。活性炭は、導電助剤やバインダーと組み合わせて使用する。導電助剤としては、黒鉛、カーボンナノチューブ等が使用できる。またバインダーとしては、ポリテトラフルオロエチレン(PTFE)、スチレンブタジエンゴム等を使用できる。
以下、アルミニウム多孔体の製造例を具体的に説明する。発泡樹脂成形体として、厚み1.6mm、気孔率95%、1インチ当たりの気孔数(セル数)約50個のウレタン発泡体を準備し、140mm×340mm角に切断した。ウレタン発泡体の表面にアルミニウムを蒸着し、厚み約1μmの導電層を形成した。
導電層を形成した樹脂成形体に金を蒸着することで厚み0.005μmの貴金属層を形成した。金を蒸発させる手段は、電子銃により電子ビームを照射する方法とした。導電層付きウレタンの周囲に不活性ガスを圧力0.01~1Paの範囲で導入し、電子ビームにより金を溶融して、導電層の表面に金薄膜を蒸着した。
表面に導電層及び貴金属層を形成したウレタン発泡体をセットした治具を整流器の陰極側に接続し、対極のアルミニウム板(純度99.99%)を陽極側に接続した。治具は、ウレタン発泡体の4辺からの給電が可能で100mm×300mmのエリアにめっき可能としたものである。温度40℃の溶融塩アルミめっき浴(67mol%AlCl3-33mol%EMIC)に浸漬し、電流密度3.6A/dm2の直流電流を90分間印加してアルミニウムをめっきした。攪拌は、テフロン(登録商標)製の回転子を用いてスターラーにて行った。なお一連の操作は、アルゴン雰囲気かつ低水分(露点-30℃以下)としたグローブボックス内で行った。また電流密度の計算では、アルミニウム多孔体の見かけの面積を使用している(ウレタン発泡体の実表面積は、見かけの面積の約8倍)。この結果、180g/m2の重量のアルミニウムめっき皮膜をほぼ均一に形成することができた。
アルミニウムめっき層を形成した発泡樹脂を温度500℃のLiCl-KCl共晶溶融塩に浸漬し、-1Vの負電位を30分間印加した。溶融塩中に気泡が発生し、ポリウレタンの分解反応が起こっていると推定された。その後大気中で室温まで冷却した後、水洗して溶融塩を除去しアルミニウム多孔体を得た。
アルミニウム多孔体の実用上の評価例として電池用電極に用いた場合を、アルミニウム箔を電極とした従来構造との比較で説明する。
(付記1)
樹脂成形体の表面に金、銀、白金、ロジウム、ルテニウム及びパラジウムからなる群より選択される1種以上の貴金属からなる導電層を形成する導電化工程と、該導電化された樹脂成形体にアルミニウムを第1の溶融塩浴中でめっきするめっき工程を有するアルミニウム構造体の製造方法であって、
前記アルミニウムめっき層が形成された樹脂成形体を第2の溶融塩に浸漬した状態で、該アルミニウムめっき層に負電位を印加しながらアルミニウムの融点以下の温度に加熱して前記樹脂成形体を分解する工程を有する、アルミニウム構造体の製造方法。
(付記2)
樹脂成形体の表面にニッケル、銅、コバルト、及び鉄からなる群より選択される1種以上の金属からなる導電層を形成する導電化工程と、該導電化された樹脂成形体にアルミニウムを溶融塩浴中でめっきするめっき工程と、前記めっき工程の後に、前記導電層を溶解する溶解工程を有するアルミニウム構造体の製造方法であって、
さらにアルミニウムめっき層が形成された樹脂成形体を溶融塩に浸漬した状態で、該アルミニウムめっき層に負電位を印加しながらアルミニウムの融点以下の温度に加熱して前記樹脂成形体を分解する工程を有する、アルミニウム構造体の製造方法。
(付記3)
樹脂成形体の表面にアルミニウムからなる導電層を形成する導電化工程と、該導電層の表面に亜鉛置換めっきを行い、亜鉛皮膜を形成する工程と、該亜鉛皮膜が形成された樹脂成形体にアルミニウムを第1の溶融塩浴中でめっきするめっき工程と、アルミニウムめっき層が形成された樹脂成形体を第2の溶融塩に浸漬した状態で、該アルミニウムめっき層に負電位を印加しながらアルミニウムの融点以下の温度に加熱して前記樹脂成形体を分解する、アルミニウム構造体の製造方法。
(付記4)
樹脂成形体の表面にアルミニウムからなる導電層を形成する導電化工程と、前記導電層の表面に金、銀、白金、ロジウム、ルテニウム及びパラジウムからなる群より選択される1種以上の貴金属を付着する工程と、該貴金属が付着した樹脂成形体にアルミニウムを第1の溶融塩浴中でめっきするめっき工程と、アルミニウムめっき層が形成された樹脂成形体を第2の溶融塩に浸漬した状態で、該アルミニウムめっき層に負電位を印加しながらアルミニウムの融点以下の温度に加熱して前記樹脂成形体を分解する、アルミニウム構造体の製造方法。
(付記5)
前記樹脂成形体は、連続した気孔を有する発泡樹脂成形体である、付記1~4のいずれか1項に記載のアルミニウム多孔体の製造方法。
(付記6)
前記めっき工程に用いる溶融塩浴は、イミダゾリウム塩浴である、付記2に記載のアルミニウム構造体の製造方法。
(付記7)
前記溶融塩浴は、有機溶媒を添加したイミダゾリウム塩浴である、付記2または6に記載のアルミニウム構造体の製造方法。
(付記8)
前記有機溶媒の添加は、めっき浴全体の25~57mol%である、付記7に記載のアルミニウム構造体の製造方法。
(付記9)
前記めっきする工程に次いで前記有機溶媒を洗浄液として用いる洗浄工程をさらに有する、付記8に記載のアルミニウム構造体の製造方法。
(付記10)
前記亜鉛置換めっきを行い、亜鉛皮膜を形成する工程は、4℃以上15℃以下の温度の亜鉛置換めっき処理液に、前記導電層が形成された樹脂成形体を浸漬して行う、付記3に記載のアルミニウム構造体の製造方法。
(付記11)
前記貴金属を付着する工程を気相法により行うことを特徴とする、付記4に記載のアルミニウム構造体の製造方法。
(付記12)
本発明により得られるアルミニウム構造体のアルミニウム表面に活物質が担持された電極材料。
(付記13)
付記12に記載の電極材料を、正極、負極の一方又は、両方に用いた電池。
(付記14)
付記12に記載の電極材料を電極として用いた電気二重層コンデンサ。
(付記15)
本発明により得られるアルミニウム構造体からなる濾過フィルタ。
(付記16)
本発明により得られるアルミニウム構造体の表面に触媒が担持された触媒担体。
21a,21b めっき槽 22 帯状樹脂 23,28 めっき浴
24 円筒状電極
25,27 正電極 26 電極ローラ
121 正極 122 負極 123 セパレータ 124 押え板
125バネ 126押圧部材 127ケース 128 正極端子
129 負極端子 130 リード線
141 分極性電極 142 セパレータ 143 有機電解液
144 リード線 145 ケース
Claims (22)
- 樹脂成形体の表面に金、銀、白金、ロジウム、ルテニウム、パラジウム、ニッケル、銅、コバルト、鉄及びアルミニウムからなる群より選択される1種以上の金属からなる導電層を形成する導電化工程と、該導電化された樹脂成形体にアルミニウムを溶融塩浴中でめっきするめっき工程とを備えるアルミニウム構造体の製造方法。
- 前記樹脂成形体は、三次元網目構造を有する樹脂多孔体である、請求項1に記載のアルミニウム構造体の製造方法。
- 前記導電化工程は、気相法により前記樹脂成形体表面に金、銀、白金、ロジウム、ルテニウム、パラジウム及びアルミニウムからなる群より選択される1種以上の金属を付着する工程である請求項1又は2に記載のアルミニウム構造体の製造方法
- 前記導電化工程は、無電解めっきにより前記樹脂成形体表面に金、銀、白金、ロジウム、ルテニウム、パラジウム、ニッケル、銅、コバルト、鉄からなる群より選択される1種以上の金属を付着する工程である、請求項1~3のいずれか1項に記載のアルミニウム構造体の製造方法。
- 前記導電化工程は、前記樹脂成形体を金、銀、白金、ロジウム、ルテニウム、パラジウム及びアルミニウムからなる群より選択される1種以上の金属を含む塗料に浸漬することで前記樹脂成形体表面に金、銀、白金、ロジウム、ルテニウム、パラジウム及びアルミニウムからなる群より選択される1種以上の金属を付着する工程である、請求項1~4のいずれか1項に記載のアルミニウム構造体の製造方法。
- 前記樹脂成形体は、ウレタンまたはメラミンである、請求項1~5のいずれか1項に記載のアルミニウム構造体の製造方法。
- 前記めっき工程の後に、さらに前記樹脂成形体を除去する工程を有する、請求項1~6のいずれか1項に記載のアルミニウム構造体の製造方法。
- 前記めっき工程の後に、前記導電層を溶解する溶解工程を有する、請求項1に記載のアルミニウム構造体の製造方法。
- 前記溶解工程と同時、または前記溶解工程の前に、前記樹脂成形体を除去する工程を有する、請求項8に記載のアルミニウム構造体の製造方法。
- 前記めっき工程の後に、前記導電層の表面に亜鉛置換めっきを行い亜鉛皮膜を形成する工程を有する、請求項1に記載のアルミニウム構造体の製造方法。
- 前記亜鉛置換めっきを行い亜鉛皮膜を形成する工程は、4℃以上15℃以下の温度の亜鉛置換めっき処理液に、前記導電層が形成された樹脂成形体を浸漬して行う、請求項10に記載のアルミニウム構造体の製造方法。
- 前記導電化工程の後に、前記導電層の表面に金、銀、白金、ロジウム、ルテニウム及びパラジウムからなる群より選択される1種以上の貴金属を付着する工程を有する、請求項1に記載のアルミニウム構造体の製造方法。
- 請求項1~12のいずれか1項に記載の製造方法により製造されたアルミニウム構造体。
- 金属層として1μm~100μmの厚さのアルミニウム層を有するアルミニウム構造体であって、該金属層は、アルミニウムの純度が90.0%以上、金、銀、白金、ロジウム、ルテニウム及びパラジウムの合計量が0.01%以上10%以下、残部不可避不純物からなるアルミニウム構造体。
- 金属層として1μm~100μmの厚さのアルミニウム層を有するアルミニウム構造体であって、該金属層は、アルミニウムの純度が80質量%以上、ニッケル、銅、コバルトおよび鉄の合計量が2質量%以上20質量%以下、残部可避不純物からなるアルミニウム構造体。
- 金属層として1μm~100μmの厚さのアルミニウム層を有するアルミニウム構造体であって、該金属層は、アルミニウムの純度が98.0質量%以上、ニッケル、銅、鉄およびコバルトの合計量が0.0001質量%以上2質量%未満、残部不可避不純物からなるアルミニウム構造体。
- 金属層として1μm~100μmの厚さのアルミニウム層を有するアルミニウム構造体であって、該金属層は、アルミニウムの純度が98.0%以上、亜鉛含有量が0.0001%以上2%以下、残部不可避不純物からなるアルミニウム構造体。
- 金属層として、一方の表面に厚み1μm~100μmの第1のアルミニウム層を、他方の表面に厚み0.05μm~1μmの第2のアルミニウム層を有し、前記2層のアルミニウム層の間に貴金属層を有するアルミニウム構造体。
- 前記金属層は、アルミニウムの純度が99.0質量%以上、金、銀、白金、ロジウム、ルテニウム及びパラジウムの合計量が0.001質量%以上1.0質量%以下、残部不可避不純物からなる請求項13に記載のアルミニウム構造体。
- さらに前記金属層を表面に備えた樹脂成形体を有する、請求項13~19のいずれか1項に記載のアルミニウム構造体。
- 前記アルミニウム層が筒状の骨格構造をなし、全体として連続した気孔を有する多孔体を形成してなる、請求項13~20のいずれか1項に記載のアルミニウム構造体。
- 前記骨格構造が略三角断面形状をなし、該三角の頂点の部分のアルミニウム層の厚さが該三角の中央部分のアルミニウム層の厚さよりも厚い形状である、請求項21に記載のアルミニウム構造体。
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- 2011-05-10 CN CN2011800049313A patent/CN102666934A/zh active Pending
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Also Published As
Publication number | Publication date |
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CA2784182A1 (en) | 2011-11-17 |
US20120070683A1 (en) | 2012-03-22 |
KR20130069539A (ko) | 2013-06-26 |
TW201207161A (en) | 2012-02-16 |
EP2570518A1 (en) | 2013-03-20 |
CN102666934A (zh) | 2012-09-12 |
US8728627B2 (en) | 2014-05-20 |
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