JP4524142B2 - Composite element - Google Patents
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- JP4524142B2 JP4524142B2 JP2004160242A JP2004160242A JP4524142B2 JP 4524142 B2 JP4524142 B2 JP 4524142B2 JP 2004160242 A JP2004160242 A JP 2004160242A JP 2004160242 A JP2004160242 A JP 2004160242A JP 4524142 B2 JP4524142 B2 JP 4524142B2
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- 239000002131 composite material Substances 0.000 title claims description 16
- 238000007747 plating Methods 0.000 claims description 104
- 239000002245 particle Substances 0.000 claims description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 26
- 238000009713 electroplating Methods 0.000 claims description 18
- 239000003990 capacitor Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000007769 metal material Substances 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 description 49
- 239000000470 constituent Substances 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910018967 Pt—Rh Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- AZUHEGMJQWJCFQ-UHFFFAOYSA-N 1,1-bis(2h-benzotriazol-4-ylmethyl)urea Chemical compound C1=CC2=NNN=C2C(CN(CC=2C3=NNN=C3C=CC=2)C(=O)N)=C1 AZUHEGMJQWJCFQ-UHFFFAOYSA-N 0.000 description 2
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- -1 nitrogen-containing compound Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- NHAZGSRLKBTDBF-UHFFFAOYSA-N 1,2,4-triazol-1-amine Chemical compound NN1C=NC=N1 NHAZGSRLKBTDBF-UHFFFAOYSA-N 0.000 description 1
- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical class C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
Description
本発明は、支持体上に電解めっき層が形成されてなり、該めっき層中に各種の機能性粉体が包埋されている複合エレメントに関する。 The present invention relates to a composite element in which an electrolytic plating layer is formed on a support, and various functional powders are embedded in the plating layer.
内燃機関から排出される排気ガスの浄化には、一般にガス流通方向に形成された多数の直通管状通路を有するコージェライトやムライト等からなるセラミック製、又は金属製のハニカム構造体のセル表面に、機能性粒子として所望の触媒を薄膜状に塗布したハニカム構造体触媒が使用されている。ハニカム構造体触媒に所望の反応特性と寿命を付与するためには、可能な限り多量の触媒成分をハニカム構造体のセル表面に塗布しなければならない。しかし、使用するコート用水性スラリーの粘度と安定性の問題から、該スラリー中の触媒成分濃度には制限がありコート回数が著しく増加するという問題がある。そこで、多量の触媒成分を少ないコート回数で経済的に塗布するためのハニカム構造体触媒の製造方法が提案されている（特許文献１参照）。 For purification of exhaust gas discharged from an internal combustion engine, a ceramic made of cordierite or mullite having a number of direct tubular passages generally formed in the gas flow direction, or a cell surface of a metal honeycomb structure, A honeycomb structure catalyst in which a desired catalyst is applied in a thin film as functional particles is used. In order to impart desired reaction characteristics and life to the honeycomb structure catalyst, as much catalyst component as possible must be applied to the cell surface of the honeycomb structure. However, due to the problems of viscosity and stability of the aqueous coating slurry to be used, there is a problem that the concentration of the catalyst component in the slurry is limited and the number of coatings is remarkably increased. Therefore, a method for manufacturing a honeycomb structure catalyst for economically applying a large amount of a catalyst component with a small number of coatings has been proposed (see Patent Document 1).
この種のハニカム構造体触媒は、高温と室温とのヒートサイクルという過酷な条件下で用いられるものなので、高機械的強度が要求されるが、その要求は未だ十分に満たされていない。また触媒成分を高分散化させることが難しく、十分な触媒性能を得ることができない。更にヒートサイクルによる熱膨張・収縮の繰り返しに起因して、長期間の使用により触媒成分がハニカム構造体から剥離するおそれがある。 Since this type of honeycomb structure catalyst is used under severe conditions such as heat cycle between high temperature and room temperature, high mechanical strength is required, but the requirement is not fully satisfied. Further, it is difficult to highly disperse the catalyst component, and sufficient catalyst performance cannot be obtained. Further, due to repeated thermal expansion and contraction due to heat cycle, the catalyst component may be peeled off from the honeycomb structure after long-term use.
これとは別に、、電気二重層キャパシタの技術においては、エネルギー密度の向上が望まれている。電気二重層キャパシタの静電容量は、電解液に接している絶縁膜の表面積に比例して増加する。そこで電気二重層キャパシタの電極には、機能性粒子として、表面積の大きな導体である活性炭が用いられている。活性炭はその表面積が１グラム当たり１０００−３０００ｍ2／ｇ程度である（特許文献２参照）。 Apart from this, in the electric double layer capacitor technology, an improvement in energy density is desired. The capacitance of the electric double layer capacitor increases in proportion to the surface area of the insulating film in contact with the electrolytic solution. Therefore, activated carbon, which is a conductor having a large surface area, is used as the functional particle for the electrode of the electric double layer capacitor. Activated carbon has a surface area of about 1000 to 3000 m 2 / g per gram (see Patent Document 2).
電気二重層キャパシタの電極は、活性炭をバインダで練ったペーストを集電体に塗布するか圧延することで得られる。この場合、活性炭の導電性が低いことから、集電体から離れて配置された活性炭は集電体との電気的導通が不十分となり、実質的に静電容量の損失が生じてしまう。また電極抵抗も高くなってしまう。そこで、ペーストにアセチレンブラックなどの導電性粒子を混合する工夫がなされている。しかし、導電性粒子を電極内に分散させたのみでは導電性粒子と活性炭との密着性が低く、電極抵抗の低減化効果は不十分である。また、活性炭の量を増やした場合、高抵抗化の原因は電極抵抗だけでなく、電解液抵抗も問題となる。活性炭の量を増やせば一層大量の電解液が必要となり、結果として電解液抵抗の増大による高抵抗化が起こるからである。 The electrode of the electric double layer capacitor can be obtained by applying or rolling a paste prepared by kneading activated carbon with a binder to a current collector. In this case, since the conductivity of the activated carbon is low, the activated carbon disposed away from the current collector is insufficient in electrical continuity with the current collector, resulting in a substantial loss of capacitance. Moreover, electrode resistance will also become high. Therefore, a device has been devised in which conductive particles such as acetylene black are mixed in the paste. However, only by dispersing the conductive particles in the electrode, the adhesion between the conductive particles and the activated carbon is low, and the effect of reducing the electrode resistance is insufficient. Further, when the amount of activated carbon is increased, the cause of the high resistance is not only the electrode resistance but also the electrolyte resistance. This is because if the amount of activated carbon is increased, a larger amount of electrolytic solution is required, and as a result, an increase in resistance due to an increase in electrolytic solution resistance occurs.
従って本発明の目的は、前述した従来技術が有する種々の欠点を解消し得る複合エレメントを提供することにある。 Accordingly, an object of the present invention is to provide a composite element that can eliminate the various drawbacks of the prior art described above.
本発明は、導電性支持体の表面に電解めっきによって形成されためっき層を有し、該めっき層中に所定の機能を有する機能性粒子が包埋されており、更に該めっき層はその表面において開孔していると共にその厚さ方向へ延びる三次元の網目状微細空隙を多数有していることを特徴とする複合エレメントを提供することにより前記目的を達成したものである。
The present invention has a plating layer formed by electrolytic plating on the surface of a conductive support, in which functional particles having a predetermined function are embedded in the plating layer, and the plating layer has its surface The above object is achieved by providing a composite element characterized in that it has a large number of three-dimensional mesh-like microvoids that are open and extend in the thickness direction.
また本発明は、前記複合エレメントの好ましい製造方法として、
導電性支持体の表面に、機能性粒子を含むスラリーを塗布して塗膜を形成し、次いで該塗膜が形成された支持体をめっき浴中に浸漬し電解めっきを施して、該粒子が包埋され且つ多数の微細空隙を有するめっき層を形成することを特徴とする複合エレメントの製造方法を提供するものである。
In addition, the present invention provides a preferable method for producing the composite element as follows:
A slurry containing functional particles is applied to the surface of the conductive support to form a coating film, and then the support on which the coating film has been formed is immersed in a plating bath and subjected to electrolytic plating. The present invention provides a method for producing a composite element, characterized in that a plating layer embedded and having a large number of fine voids is formed.
また本発明は、電解めっきによって形成されためっき層を有し、該めっき層中に所定の機能を有する機能性粒子が包埋されており、更に該めっき層はその表面において開孔していると共にその厚さ方向へ延びる三次元の網目状微細空隙を多数有していることを特徴とする複合エレメントを提供するものである。 The present invention also includes a plating layer formed by electrolytic plating, in which functional particles having a predetermined function are embedded in the plating layer, and the plating layer is open on the surface thereof. In addition, the present invention provides a composite element characterized by having a large number of three-dimensional network-like fine voids extending in the thickness direction.
更に本発明は、前記複合エレメントの好ましい製造方法として、
導電性支持体の表面に剥離層を形成し、その上に機能性粒子を含むスラリーを塗布して塗膜を形成し、次いで該塗膜が形成された支持体をめっき浴中に浸漬し電解めっきを施して、該粒子が包埋され且つ多数の微細空隙を有するめっき層を形成し、該めっき層の形成後に、前記支持体から該めっき層を剥離することを特徴とする複合エレメントの製造方法を提供するものである。
Furthermore, the present invention provides a preferable method for producing the composite element as follows:
A release layer is formed on the surface of the conductive support, a slurry containing functional particles is applied thereon to form a coating film, and then the support on which the coating film has been formed is immersed in a plating bath for electrolysis. A composite element is produced by performing plating to form a plating layer in which the particles are embedded and having a large number of fine voids, and after the formation of the plating layer, the plating layer is peeled off from the support. A method is provided.
本発明の複合エレメントは、これを種々の用途に用いることで様々な利点が生じる。例えば内燃機関から排出される排気ガスの浄化に用いると、簡単な操作で多量の触媒を支持体に担持させることができる。また、熱膨張に起因する触媒の脱落を防止することができる。電気二重層キャパシタの電極として用いると、電極全体の抵抗を下げることができ、キャパシタのエネルギー密度を高めることができる。 The composite element of the present invention has various advantages when used in various applications. For example, when used for purifying exhaust gas discharged from an internal combustion engine, a large amount of catalyst can be supported on a support by a simple operation. Further, it is possible to prevent the catalyst from falling off due to thermal expansion. When used as an electrode of an electric double layer capacitor, the resistance of the entire electrode can be reduced, and the energy density of the capacitor can be increased.
以下本発明を、その好ましい実施形態に基づき図面を参照しながら説明する。先ず第１の実施形態として、本発明を内燃機関から排出される排気ガスの浄化に用いる例を説明する。図１は、本発明の一実施形態としての触媒エレメントの要部を拡大して示す模式図である。触媒エレメント１は、支持体２と、その表面に電解めっきによって形成されためっき層３とを備えている。めっき層３中には、機能性粒子の一種である触媒の粒子４が包埋されている。めっき層３は多数の微細空隙５を有している。微細空隙５は、めっき層３の厚さ方向へ延びており、めっき層３の表面において開孔している。
The present invention will be described below based on preferred embodiments with reference to the drawings. First, as a first embodiment, an example in which the present invention is used for purifying exhaust gas discharged from an internal combustion engine will be described. FIG. 1 is a schematic view showing an enlarged main part of a catalyst element as one embodiment of the present invention. The
支持体２としては導電性を有するものが用いられる。そのような支持体の例としては、例えば金属材料のように材料そのものが導電性を有するものや、母材自体は導電性を有さないが、その表面に無電解めっき等によって導電性を付与したものを用いることができる。また、触媒エレメントは、酸素濃度の高い高温の排気ガスの浄化に用いられるものなので、支持体２は耐酸化性等の耐腐食性材料から構成されていることが好ましい。これらを勘案すると、ステンレスなどの導電性を有し且つ耐腐食性を有する金属材料を用いることが特に好ましい。 As the support 2, one having conductivity is used. Examples of such a support include, for example, a metal material that is electrically conductive, such as a metal material, or a base material that is not electrically conductive, but imparts conductivity to the surface by electroless plating or the like. Can be used. Further, since the catalyst element is used for purifying high-temperature exhaust gas having a high oxygen concentration, the support 2 is preferably made of a corrosion-resistant material such as oxidation resistance. Considering these, it is particularly preferable to use a metal material having conductivity and corrosion resistance such as stainless steel.
支持体２の形状に特に制限はない。例えば従来の触媒エレメントに用いられているようなハニカム構造体であってもよい。或いは平板状であってもよい。 There is no restriction | limiting in particular in the shape of the support body 2. As shown in FIG. For example, a honeycomb structure as used in a conventional catalyst element may be used. Alternatively, it may be flat.
めっき層３中に包埋されている触媒の粒子４としては排気ガス中に含まれている各種ガス、例えば一酸化炭素（ＣＯ）、窒素酸化物（ＮＯｘ）、ハイドロカーボン類（ＨＣ）の分解に対する触媒作用を有するものが用いられる。そのような触媒の粒子４としては、従来この種の分野に用いられているものを特に制限なく用いることができる。例えばアルミナ粒子からなる担体に担持させたルテニウム−白金触媒（以下、Pt-Rh/Al2O3ともいう）や、セリウム−ジルコニウム系複合酸化物からなる担体に担持させたルテニウム−白金触媒（以下、Pt-Rh/CZともいう）などを用いることができる。また、Ｃａ2ＭｎＯ4やＣａ2Ｍｎ0.95Ｐｄ0.5Ｏ4などのマンガン酸化物系触媒を用いることもできる。特にマンガン酸化物系触媒は導電性を有するので、後述する触媒エレメントの製造方法において、触媒の粒子４を含むスラリー中に導電性の粒子６を含有させる必要がないという利点がある。以上の触媒は一種又は二種以上を組み合わせて用いることができる。
As the catalyst particles 4 embedded in the plating layer 3, various gases contained in the exhaust gas, for example, carbon monoxide (CO), nitrogen oxide (NOx), and hydrocarbons (HC) are decomposed. Those having a catalytic action on the above are used. As such catalyst particles 4, those conventionally used in this type of field can be used without particular limitation. For example, a ruthenium-platinum catalyst (hereinafter also referred to as Pt-Rh / Al2O3) supported on a support made of alumina particles, or a ruthenium-platinum catalyst (hereinafter referred to as Pt--) supported on a support made of a cerium-zirconium composite oxide. Rh / CZ) can also be used. Further, manganese oxide catalysts such as Ca 2 MnO 4 and Ca 2 Mn 0.95 Pd 0.5 O 4 can also be used. In particular, since the manganese oxide-based catalyst has conductivity, there is an advantage that it is not necessary to include the
触媒の粒子４は、めっき層３中に包埋されている。この場合、触媒の粒子４は、完全にめっき層３中に包埋されていることを要せず、その一部はめっき層３の表面に露出していてもよい。 The catalyst particles 4 are embedded in the plating layer 3. In this case, the catalyst particles 4 do not need to be completely embedded in the plating layer 3, and a part thereof may be exposed on the surface of the plating layer 3.
触媒の粒子４の大きさは本発明において臨界的なものではなく、従来用いられてきたものと同様とすることができる。例えば担体に担持された状態の触媒においては、担体の粒径は０．０１〜１００μｍ、特に０．１〜１０μｍ程度とすることができる。担体に担持されているルテニウムや白金の粒子の粒径はこれよりも小さく、０．５〜１０００ｎｍ、特に１〜１００ｎｍ程度である。 The size of the catalyst particles 4 is not critical in the present invention, and may be the same as that conventionally used. For example, in a catalyst supported on a carrier, the particle size of the carrier can be about 0.01 to 100 μm, particularly about 0.1 to 10 μm. The particle diameter of ruthenium or platinum particles supported on the carrier is smaller than this, and is about 0.5 to 1000 nm, particularly about 1 to 100 nm.
めっき層３は先に述べた通り電解めっきによって形成されている。めっき層３を構成する材料は電解めっき可能な材料であればその種類に特に制限はない。特に、めっき層３を構成する材料が、排気ガス中に含まれている各種ガスの分解に対する触媒作用を有していると、排気ガスの浄化効果が一層高まるので好ましい。そのような材料としては、金属材料及び酸化物材料が挙げられる。金属材料としては銅、ニッケル、コバルトなどを用いることができる。酸化物材料としては二酸化マンガンなどを用いることができる。 The plating layer 3 is formed by electrolytic plating as described above. If the material which comprises the plating layer 3 is a material which can be electroplated, there will be no restriction | limiting in particular in the kind. In particular, it is preferable that the material constituting the plating layer 3 has a catalytic action against the decomposition of various gases contained in the exhaust gas because the purification effect of the exhaust gas is further enhanced. Such materials include metal materials and oxide materials. As the metal material, copper, nickel, cobalt, or the like can be used. Manganese dioxide or the like can be used as the oxide material.
めっき層３は、触媒の粒子４を十分に三次元的に分散させるのに足る厚みを有している。しかし、めっき層３の厚みが大きくなると、その分、使用する触媒の粒子４の量も多くなり経済的でなくなる。これらを勘案すると、めっき層の厚みは０．３〜２０μｍ、特に０．３〜１０μｍ、とりわけ０．５〜５μｍ程度の薄層であることが好ましい。 The plating layer 3 has a thickness sufficient to sufficiently disperse the catalyst particles 4 three-dimensionally. However, when the thickness of the plating layer 3 is increased, the amount of catalyst particles 4 to be used is increased accordingly, which is not economical. Considering these, the thickness of the plating layer is preferably 0.3 to 20 μm, particularly 0.3 to 10 μm, and particularly preferably a thin layer of about 0.5 to 5 μm.
めっき層３に形成されている微細空隙５は、これを通じてガスをめっき層３の内部にまで供給してその分解を生じせしめるためのものである。この目的のために、微細空隙５は、めっき層３の表面における開孔面積が平均して０．１〜５０μｍ2、特に１〜１０μｍ2であることが好ましい。微細空隙５はめっき層３の表面においてほぼ均一に開孔している。微細空隙５の開孔率、即ちめっき層３の面積に対する開孔面積の総和の割合は０．１〜２０％、特に２〜２０％であり、とりわけ５〜１０％であることが好ましい。開孔面積及び開孔率は、めっき層３の表面を電子顕微鏡観察し、画像解析から求めることができる。更に、めっき層３は、その表面を電子顕微鏡観察により平面視したときに、どのような観察視野をとっても、１００μｍ×１００μｍの正方形の視野範囲内に１〜２００００個、特に１００〜２０００個の微細空隙５が存在していることが好ましい。 The fine voids 5 formed in the plating layer 3 are for supplying gas to the inside of the plating layer 3 through this and causing the decomposition thereof. For this purpose, the micropores 5, 0.1 to 50 [mu] m 2 open area in the surface of the plating layer 3 on average, particularly preferably 1 to 10 [mu] m 2. The fine voids 5 are almost uniformly opened on the surface of the plating layer 3. The aperture ratio of the fine voids 5, that is, the ratio of the total aperture area to the area of the plating layer 3 is 0.1 to 20%, particularly 2 to 20%, and particularly preferably 5 to 10%. The hole area and the hole area ratio can be obtained from image analysis by observing the surface of the plating layer 3 with an electron microscope. Furthermore, the plating layer 3 has a fine field of 1 to 20000, particularly 100 to 2000, within a square field of view of 100 μm × 100 μm, regardless of the observation field when the surface is viewed in plan by electron microscope observation. It is preferable that the gap 5 exists.
先に述べた通り、微細空隙５はめっき層３の厚さ方向へ延びている。微細空隙５は、めっき層３を貫き支持体２まで達しているものもあれば、めっき層３の途中で終端しているものもある。また、二以上の微細空隙５が交差している場合もある。微細空隙５は一般に曲折しながらめっき層３の厚さ方向へ延びている。微細空隙５の存在によってめっき層３中には三次元の網目状構造が形成されている。この網目状構造によってめっき層３は十分なガス浸透性を有するようになる。このような構造を有する微細空隙５の形成方法については後述する。 As described above, the fine gap 5 extends in the thickness direction of the plating layer 3. Some of the fine voids 5 penetrate through the plating layer 3 and reach the support 2, and some of the fine voids 5 terminate in the middle of the plating layer 3. In some cases, two or more fine voids 5 intersect each other. The fine gap 5 generally extends in the thickness direction of the plating layer 3 while being bent. A three-dimensional network structure is formed in the plating layer 3 due to the presence of the fine voids 5. With this network structure, the plating layer 3 has sufficient gas permeability. A method for forming the fine void 5 having such a structure will be described later.
触媒の粒子４に加えて、めっき層３中には導電性の粒子６が含まれていてもよい。これによって電解めっきによるめっき層３の形成を効率的に行うことができる。尤も、触媒の粒子４として導電性を有するものを用いる場合には、導電性の粒子６を用いなくてもめっき層３を首尾良く形成することができる。導電性の粒子６としては、炭素材料の粒子や金属酸化物の粒子などが挙げられる。炭素材料としては、例えば、ファーネスブラック、チャンネルブラック及びアセチレンブラック等のカーボンブラックや、活性炭、黒鉛等が挙げられる。金属酸化物の粒子としては、例えば二酸化マンガンやマグネタイトの粒子を用いることができる。これらの粒子は単独あるいは混合して使用することができる。特に、導電性の粒子６としては、導電性と共に各種ガスの分解に対する触媒作用を有している材料である二酸化マンガンやマグネタイトの粒子を用いることが好ましい。
In addition to the catalyst particles 4, the plating layer 3 may contain
以上の構成を有する触媒エレメント１によれば、触媒の粒子４間がめっき層３の構成材料によって結合されているので機械的強度が高くなる。特に、１０００℃程度の高温と室温とのヒートサイクルの激しい過酷な条件下で使用されても、触媒の粒子４の脱落が起こりにくい。この脱落を一層効果的に防止する観点から、めっき層３の構成材料は、その熱膨張係数が、支持体２の構成材料の熱膨張係数と、触媒の粒子４の熱膨張係数（担持されている場合には担体の熱膨張係数）との中間であることが好ましい。
According to the
更に本実施形態の触媒エレメント１によれば、使用を繰り返しても触媒の粒子４の分散状態が維持される。その結果、従来では分散状態が悪く結晶子径が大きいために不可能であった低温においてもＣＯ、ＮＯｘ、ＨＣ、水素分子、酸素分子等の解離を容易に起こすことができる。
Furthermore, according to the
次に、本実施形態の触媒エレメント１の好ましい製造方法について説明する。先ず、支持体２の表面に電解めっきによってめっき層３を形成する。電解めっきの手順は次の通りである。
Next, the preferable manufacturing method of the
先ず、触媒の粒子４を含むスラリーを調製する。スラリーは、触媒の粒子に加えて水やエタノールなど希釈溶媒を含み、更に必要に応じて、先に述べた導電性の粒子６を含んでいる。このスラリーを支持体２の表面に塗布し塗膜を形成する。表面に塗膜が形成された支持体２をめっき浴中に浸漬して電解めっきを施す。これによってめっき層３が形成される。先に述べた通り、めっき層３の構成材料としては、金属材料又は酸化物材料が好ましく用いられる。この場合、めっき層３として、金属材料又は酸化物材料を含む層を単独で形成してもよく、或いは初めに酸化物材料を含む下層めっき層を形成し、その上に金属材料を含む上層めっき層を形成してもよい。めっき層３をこのような２層構造とすることで、金属材料中の電子が酸化物材料へと移行しやすくなり、電子の授受が容易になることから、酸化還元反応の触媒性能が向上するという利点が生じる。
First, a slurry containing catalyst particles 4 is prepared. The slurry includes a diluting solvent such as water and ethanol in addition to the catalyst particles, and further includes the
めっき層３の構成材料が、各種ガスの分解に対する触媒作用を有するものである場合、その触媒活性はめっき条件によって左右される。具体的には電解時の電流密度、イオン濃度、電解時間等の条件を調整することが重要である。また、これらの条件は、めっき層３に所望の微細空隙５を形成する観点からも重要である。 When the constituent material of the plating layer 3 has a catalytic action against the decomposition of various gases, the catalytic activity depends on the plating conditions. Specifically, it is important to adjust conditions such as current density, ion concentration, and electrolysis time during electrolysis. These conditions are also important from the viewpoint of forming desired fine voids 5 in the plating layer 3.
例えばめっき層３の構成材料として金属材料であるニッケルを用いる場合の電解めっきの条件としては、例えばワット浴やスルファミン浴を用いることができる。ワット浴の組成は例えば硫酸ニッケルが１５０〜３５０ｇ／ｌ、塩化ニッケルが２０〜７０ｇ／ｌ、ホウ酸が１０〜５０ｇ／ｌである。ワット浴の浴温は３０〜８０℃、電解時の電流密度は０．５〜１００Ａ／ｄｍ2とすることができる。スルファミン酸浴を用いる場合の浴温は４０〜６０℃程度であり、電流密度はワット浴の場合と同様とすることができる。金属材料であるコバルトを用いる場合の電解めっきの条件としては、浴組成は、塩化コバルト或いは硫酸コバルトを１〜５０ｇ／ｌ含む水溶液とすることができる。浴温は４０〜６０℃とし、電解時の電流密度は１〜１０Ａ／ｄｍ2とすることができる。金属材料である銅を用いる場合、硫酸銅系溶液を用いるときには、銅の濃度を３０〜１００ｇ／ｌ、硫酸の濃度を５０〜２００ｇ／ｌ、塩素の濃度を３０ｐｐｍ以下とし、液温を３０〜８０℃、電流密度を１〜１００Ａ／ｄｍ2とすればよい。ピロ燐酸銅系溶液を用いる場合には、銅の濃度２〜５０ｇ／ｌ、ピロ燐酸カリウムの濃度１００〜７００ｇ／ｌとし、液温を３０〜６０℃、ｐＨを８〜１２、電流密度を１〜１０Ａ／ｄｍ2とすればよい。酸化物材料である二酸化マンガンを用いる場合の電解めっきの条件としては、浴組成は、硫酸マンガンを１００〜３００ｇ／ｌである。浴温は３０〜９０℃、電解時の電流密度は０．５〜１００Ａ／ｄｍ2とすることができる。このような条件で電解めっきを行うことで、めっき層に所望の微細空隙を形成することができる。 For example, as a condition of electroplating when nickel, which is a metal material, is used as the constituent material of the plating layer 3, for example, a watt bath or a sulfamine bath can be used. The composition of the Watt bath is, for example, 150 to 350 g / l of nickel sulfate, 20 to 70 g / l of nickel chloride, and 10 to 50 g / l of boric acid. The bath temperature of the Watt bath can be 30 to 80 ° C., and the current density during electrolysis can be 0.5 to 100 A / dm 2 . When the sulfamic acid bath is used, the bath temperature is about 40 to 60 ° C., and the current density can be the same as that of the watt bath. As a condition for electrolytic plating when using cobalt which is a metal material, the bath composition can be an aqueous solution containing 1 to 50 g / l of cobalt chloride or cobalt sulfate. The bath temperature can be 40 to 60 ° C., and the current density during electrolysis can be 1 to 10 A / dm 2 . When copper, which is a metal material, is used, when using a copper sulfate solution, the copper concentration is 30 to 100 g / l, the sulfuric acid concentration is 50 to 200 g / l, the chlorine concentration is 30 ppm or less, and the liquid temperature is 30 to 30 ppm. What is necessary is just to make 80 degreeC and a current density into 1-100 A / dm < 2 >. When using a copper pyrophosphate solution, the concentration of copper is 2 to 50 g / l, the concentration of potassium pyrophosphate is 100 to 700 g / l, the liquid temperature is 30 to 60 ° C., the pH is 8 to 12, and the current density is 1. ~10A / dm 2 and may be set. As a condition of electrolytic plating when using manganese dioxide which is an oxide material, the bath composition is 100 to 300 g / l of manganese sulfate. The bath temperature can be 30 to 90 ° C., and the current density during electrolysis can be 0.5 to 100 A / dm 2 . By performing electrolytic plating under such conditions, desired fine voids can be formed in the plating layer.
次に、本発明の第２の実施形態について説明する。この実施形態に関し特に説明しない点については、第１の実施形態に関して詳述した説明が適宜適用される。第２の実施形態は、本発明を電気二重層キャパシタの電極に適用した例である。本実施形態においては、機能性粒子として活性炭が用いられる。本実施形態の電極の構造は、機能性粒子の種類やめっき層の構成材料が異なる以外は、第１の実施形態に関して図１に示したエレメントとほぼ同様である。めっき層の構成材料としては例えば銅、ニッケル、アルミニウムなどが用いられる。 Next, a second embodiment of the present invention will be described. For points not specifically described with respect to this embodiment, the description detailed with respect to the first embodiment is applied as appropriate. The second embodiment is an example in which the present invention is applied to an electrode of an electric double layer capacitor. In the present embodiment, activated carbon is used as the functional particles. The structure of the electrode of this embodiment is almost the same as the element shown in FIG. 1 with respect to the first embodiment, except that the type of functional particles and the constituent material of the plating layer are different. For example, copper, nickel, aluminum or the like is used as a constituent material of the plating layer.
本実施形態の電極においては、活性炭は導電性の高い材料から構成されているめっき層中に包埋されている。従って、活性炭を含むペーストを支持体に塗布して形成される従来の電極に比較して、電極全体の抵抗を下げることができる。なお、活性炭の表面がめっき層の構成材料で被覆されてしまうことで、活性炭が電解液と接する表面積が減少してしまうという懸念がある。しかし、活性炭の表面積のうち表面部分は僅かであることから、その部分が被覆されたとしても全表面積に及ぼす影響は微々たるものであり、実質的な問題は生じない。なお、活性炭としては、従来この種のキャパシタに用いられてきたものと同様のものを特に制限なく用いることができる。 In the electrode of the present embodiment, activated carbon is embedded in a plating layer made of a highly conductive material. Therefore, the resistance of the entire electrode can be reduced as compared with a conventional electrode formed by applying a paste containing activated carbon to a support. In addition, there exists a concern that the surface area which activated carbon contacts with electrolyte solution will decrease because the surface of activated carbon will be coat | covered with the constituent material of a plating layer. However, since the surface portion of the surface area of the activated carbon is very small, even if the portion is coated, the influence on the total surface area is insignificant, and no substantial problem occurs. In addition, as activated carbon, the thing similar to what was conventionally used for this kind of capacitor can be especially used without a restriction | limiting.
本実施形態の電極は、従来用いられてきた電極に比較して電解液抵抗を下げる効果を有していることも特徴の一つである。従来の電極では、活性炭同士の間に必要量以上の電解液が存在しており、それによる電解液抵抗の増大の問題が生じていた。これに対して本実施形態の電極では、活性炭同士の間に存在する無駄な空間の大半をめっき層が埋めているので、活性炭の極く近接した領域にしか電解液が存在せず、電解液抵抗を下げることができる。 One feature of the electrode of the present embodiment is that it has an effect of lowering the resistance of the electrolytic solution as compared with a conventionally used electrode. In the conventional electrode, an amount of electrolyte more than the necessary amount exists between the activated carbons, which causes a problem of an increase in electrolyte resistance. On the other hand, in the electrode of the present embodiment, since the plating layer fills most of the useless space existing between the activated carbons, the electrolytic solution is present only in the very close region of the activated carbon. Resistance can be lowered.
更に本実施形態の電極では、活性炭がめっき層中に包埋されているので耐衝撃性が高い。従って該電極を備えた電気二重層キャパシタは、自動車に積載される電源等として特に有用である。 Furthermore, in the electrode of this embodiment, since activated carbon is embedded in the plating layer, impact resistance is high. Therefore, the electric double layer capacitor provided with the electrode is particularly useful as a power source mounted on an automobile.
本実施形態の電極は支持体の表面にめっき層を有するものであるが、これに代えてめっき層を支持体から剥離し、単独のめっき層を電極として用いることもできる。支持体は電気二重層キャパシタにおける静電容量には寄与しないので、キャパシタの高容量密度化を妨げる要因となっていた。しかし、本実施形態のように単独のめっき層を電極として用いることで、従来のキャパシタに比較して高容量密度化を図ることができる。またキャパシタの小型化を図ることもできる。更に、単独のめっき層からなる電極は、それ自体が集電体として機能することから、従来の電極と比較して活性炭の層を厚く形成しても、電極抵抗の増大が起こらないので、静電容量の大きなキャパシタを得ることができる。 Although the electrode of this embodiment has a plating layer on the surface of a support body, it replaces with this and can peel a plating layer from a support body and can also use a single plating layer as an electrode. Since the support does not contribute to the capacitance in the electric double layer capacitor, it has been a factor that hinders the increase in the capacitance density of the capacitor. However, by using a single plating layer as an electrode as in the present embodiment, a higher capacity density can be achieved as compared with a conventional capacitor. Further, the size of the capacitor can be reduced. Furthermore, since an electrode composed of a single plating layer itself functions as a current collector, even if an activated carbon layer is formed thicker than a conventional electrode, an increase in electrode resistance does not occur. A capacitor having a large capacitance can be obtained.
支持体の表面にめっき層を有する電極は、第１の実施形態のエレメントと同様の方法で製造することができる。支持体からめっき層を剥離して、めっき層単独の電極を製造する場合には、支持体の表面に予め剥離層を形成し、その後に活性炭を含むスラリーを塗布すればよい。剥離層に用いられる物質としては、例えば有機化合物を用いることが好ましく、特に窒素含有化合物又は硫黄含有化合物を用いることが好ましい。窒素含有化合物としては、例えばベンゾトリアゾール（ＢＴＡ）、カルボシキベンゾトリアゾール（ＣＢＴＡ）、トリルトリアゾール（ＴＴＡ）、Ｎ’，Ｎ’−ビス（ベンゾトリアゾリルメチル）ユリア（ＢＴＤ−Ｕ）及び３−アミノ−１Ｈ−１，２，４−トリアゾール（ＡＴＡ）などのトリアゾール系化合物が好ましく用いられる。硫黄含有化合物としては、メルカプトベンゾチアゾール（ＭＢＴ）、チオシアヌル酸（ＴＣＡ）および２−ベンズイミダゾールチオール（ＢＩＴ）などが挙げられる。有機化合物に代えて、クロム酸化物等の金属系被膜によっても同様の効果を得ることができる。 An electrode having a plating layer on the surface of the support can be produced by the same method as the element of the first embodiment. When the plating layer is peeled from the support to produce an electrode having a single plating layer, a peeling layer may be formed on the surface of the support in advance, and then a slurry containing activated carbon may be applied. As the substance used for the release layer, for example, an organic compound is preferably used, and a nitrogen-containing compound or a sulfur-containing compound is particularly preferably used. Examples of the nitrogen-containing compound include benzotriazole (BTA), carboxyl benzotriazole (CBTA), tolyltriazole (TTA), N ′, N′-bis (benzotriazolylmethyl) urea (BTD-U) and 3- Triazole compounds such as amino-1H-1,2,4-triazole (ATA) are preferably used. Examples of the sulfur-containing compound include mercaptobenzothiazole (MBT), thiocyanuric acid (TCA), 2-benzimidazolethiol (BIT), and the like. The same effect can be obtained by using a metallic coating such as chromium oxide instead of the organic compound.
本実施形態の電極（支持体あり及びなしの場合を含む）を用いて電気二重層キャパシタを製造する手順は次の通りである。先ず電極を電解液に含浸させた後、セパレータを挟んで２つの電極を樹脂製ガスケットと共にかしめることにより封口する。電解液としては有機系のもの及び水系のものを用いることができる。有機系電解液としては、例えば第四級アンモニウム塩をプロピレンカーボネート等の有機溶媒に溶解したものが用いられる。水系の電解液としては硫酸水溶液が用いられる。低抵抗化を考慮すると有機系電解液を用いることが好ましい。製造工程の簡略化の点からは水系電解液を用いることが好ましい。 The procedure for manufacturing the electric double layer capacitor using the electrode of this embodiment (including the case with and without the support) is as follows. First, an electrode is impregnated with an electrolytic solution, and then sealed by caulking the two electrodes together with a resin gasket with a separator interposed therebetween. As the electrolytic solution, an organic type or an aqueous type can be used. As the organic electrolyte, for example, a solution in which a quaternary ammonium salt is dissolved in an organic solvent such as propylene carbonate is used. A sulfuric acid aqueous solution is used as the aqueous electrolyte. In view of reducing resistance, it is preferable to use an organic electrolyte. From the viewpoint of simplification of the manufacturing process, it is preferable to use an aqueous electrolyte.
以下実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲はかかる実施例に制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples.
〔実施例１〜１８並びに比較例１及び２〕
ステンレス製のハニカム構造体からなる支持体の表面に、Pt-Rh/Al2O3、Pt-Rh/CZ、及び導電性の粒子を含むスラリーを塗布し塗膜を形成した。スラリー中におけるこれら三者の重量比は、これら三者の合計量に対して表２に示す通りの値であった。Pt-Rh/Al2O3におけるAl2O3の粒径は０．２μｍで、Pt-Rh/CZにおけるCZの粒径は１０μｍであった。導電性の粒子のうち、グラファイトの粒径は０．８μｍ、ＭｎＯ2の粒径は１０μｍ、Ｆｅ3Ｏ4（マグネタイト）の粒径は０．２μｍであった。
[Examples 1 to 18 and Comparative Examples 1 and 2]
A slurry containing Pt—Rh / Al 2 O 3, Pt—Rh / CZ and conductive particles was applied to the surface of a support made of a stainless steel honeycomb structure to form a coating film. The weight ratio of these three components in the slurry was as shown in Table 2 with respect to the total amount of these three components. The particle size of Al2O3 in Pt—Rh / Al2O3 was 0.2 μm, and the particle size of CZ in Pt—Rh / CZ was 10 μm. Of the conductive particles, graphite had a particle size of 0.8 μm, MnO 2 had a particle size of 10 μm, and Fe 3 O 4 (magnetite) had a particle size of 0.2 μm.
塗膜が形成された支持体をめっき浴中に浸漬し、電解めっきを行いめっき層を形成した。但し、比較例１及び２ではめっきを行っていない。めっき層の構成材料は表２に示す通りである。めっき条件は次の通りであった。形成されためっき層の厚みは実施例及び比較例を通じて同一の１０μｍとした。得られためっき層を電子顕微鏡観察したところ、微細空隙の存在が確認された。微細空隙の平均開孔面積は１μｍ2であり、開孔率は３０％であった。 The support on which the coating film was formed was immersed in a plating bath and subjected to electrolytic plating to form a plating layer. However, in Comparative Examples 1 and 2, no plating was performed. The constituent materials of the plating layer are as shown in Table 2. The plating conditions were as follows. The formed plating layer had the same thickness of 10 μm throughout the examples and comparative examples. When the obtained plating layer was observed with an electron microscope, the presence of fine voids was confirmed. The average open area of the fine voids was 1 μm 2 and the open area ratio was 30%.
〔めっき層がＭｎＯ2の場合〕
・めっき浴；硫酸マンガン １５０ｇ／ｌ
・浴温；８５℃
・電流密度；４Ａ／ｄｍ2
[When the plating layer is MnO 2 ]
・ Plating bath: Manganese sulfate 150g / l
・ Bath temperature: 85 ℃
・ Current density: 4 A / dm 2
〔めっき層がＣｕの場合〕
・めっき浴；硫酸銅 １５０ｇ／ｌ
・浴温；５０℃
・電流密度；１０Ａ／ｄｍ2
[When the plating layer is Cu]
・ Plating bath: Copper sulfate 150g / l
・ Bath temperature: 50 ℃
・ Current density: 10 A / dm 2
〔めっき層がＮｉの場合〕
・めっき浴；硫酸ニッケル １５０ｇ／ｌ
・浴温；５０℃
・電流密度；１０Ａ／ｄｍ2
[When the plating layer is Ni]
・ Plating bath: Nickel sulfate 150g / l
・ Bath temperature: 50 ℃
・ Current density: 10 A / dm 2
〔めっき層がＣｏの場合〕
・めっき浴；硫酸コバルト １５０ｇ／ｌ
・浴温；５０℃
・電流密度；１０Ａ／ｄｍ2
[When the plating layer is Co]
・ Plating bath: Cobalt sulfate 150g / l
・ Bath temperature: 50 ℃
・ Current density: 10 A / dm 2
〔性能評価〕
実施例及び比較例で得られた触媒エレメントについて、以下の方法で三点曲げ強度及びガスの浄化性能を評価した。それらの結果を表２に示す。
[Performance evaluation]
About the catalyst element obtained by the Example and the comparative example, the three-point bending strength and the gas purification performance were evaluated with the following method. The results are shown in Table 2.
〔三点曲げ強度〕
ＪＩＳ Ｒ １６０１「ファインセラミックスの曲げ強さの試験法」に準拠した三点曲げ法により曲げ強度試験を行った。試料の大きさは５ｍｍ×６ｍｍ×３０ｍｍとした。
[Three-point bending strength]
A bending strength test was performed by a three-point bending method in accordance with JIS R 1601 “Testing method for bending strength of fine ceramics”. The sample size was 5 mm × 6 mm × 30 mm.
〔ガスの浄化性能〕
初期状態及び耐久後の状態の触媒エレメントについてガスの浄化性能を評価した。モデルガスとして以下の表１に示すリッチガス及びリーンガスを用いた。
[Gas purification performance]
The gas purification performance of the catalyst element in the initial state and the state after durability was evaluated. Rich gas and lean gas shown in Table 1 below were used as model gas.
初期状態においては、モデルガスを室温から昇温し、ＮＯ、ＣＯ、ＨＣ（Ｃ3Ｈ6＋Ｃ3Ｈ8）のそれぞれが初期濃度の５０％に低下した温度を測定し、その温度を浄化５０％温度とした。リッチガスとリーンガスはそれぞれ１秒毎に切り換えた。触媒を通るガス流の空間速度（ＳＶ）は３００００／時間とした。この温度が低いほど触媒活性が高いことを意味する。耐久後においては、リッチガスとリーンガスを５秒毎に切り換えて９００℃で３０分、７５０℃で３０分のサイクルを１５回繰り返し、その後に前記の手順で浄化５０％温度を測定した。初期招待と耐久後の状態での浄化５０％温度の差が小さいほど触媒活性が高いことを意味する。 In the initial state, the model gas is heated from room temperature, and the temperature at which NO, CO, and HC (C 3 H 6 + C 3 H 8 ) are each reduced to 50% of the initial concentration is measured, and the temperature is purified 50 % Temperature. Rich gas and lean gas were switched every second. The space velocity (SV) of the gas flow through the catalyst was 30000 / hour. A lower temperature means higher catalytic activity. After the endurance, the rich gas and the lean gas were switched every 5 seconds, and a cycle of 900 ° C. for 30 minutes and 750 ° C. for 30 minutes was repeated 15 times, and then the purified 50% temperature was measured by the above procedure. The smaller the difference between the initial invitation and the 50% purification temperature after the endurance, the higher the catalytic activity.
表２に示す結果から明らかなように、各実施例のエレメントは各比較例のエレメントに比較して曲げ強度が高いことが判る。また触媒活性が高いことが判る。 As is apparent from the results shown in Table 2, it can be seen that the elements of each example have higher bending strength than the elements of each comparative example. It can also be seen that the catalytic activity is high.
１ 触媒エレメント
２ 支持体
３ めっき層
４ 触媒の粒子
５ 微細空隙
６ 導電性の粒子
DESCRIPTION OF
Claims (10)
導電性支持体の表面に、機能性粒子を含むスラリーを塗布して塗膜を形成し、次いで該塗膜が形成された支持体をめっき浴中に浸漬し電解めっきを施して、該粒子が包埋され且つ多数の微細空隙を有するめっき層を形成することを特徴とする複合エレメントの製造方法。 A method for producing a composite element according to claim 1,
A slurry containing functional particles is applied to the surface of the conductive support to form a coating film, and then the support on which the coating film has been formed is immersed in a plating bath and subjected to electrolytic plating. A method of manufacturing a composite element, comprising forming a plating layer embedded and having a large number of fine voids.
導電性支持体の表面に剥離層を形成し、その上に機能性粒子を含むスラリーを塗布して塗膜を形成し、次いで該塗膜が形成された支持体をめっき浴中に浸漬し電解めっきを施して、該粒子が包埋され且つ多数の微細空隙を有するめっき層を形成し、該めっき層の形成後に、前記支持体から該めっき層を剥離することを特徴とする複合エレメントの製造方法。 A method for producing a composite element according to claim 8,
A release layer is formed on the surface of the conductive support, a slurry containing functional particles is applied thereon to form a coating film, and then the support on which the coating film has been formed is immersed in a plating bath for electrolysis. A composite element is produced by performing plating to form a plating layer in which the particles are embedded and having a large number of fine voids, and after the formation of the plating layer, the plating layer is peeled off from the support. Method.
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| JP7353810B2 (en) * | 2019-06-17 | 2023-10-02 | 古河電気工業株式会社 | Composite material, exhaust gas purification catalyst, and method for producing composite material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5884988A (en) * | 1981-11-12 | 1983-05-21 | Toagosei Chem Ind Co Ltd | Production of catalyst for cathode |
| JPS62114619A (en) * | 1985-11-12 | 1987-05-26 | Cataler Kogyo Kk | Catalyst filter for removing particulate |
| JPH0549945A (en) * | 1991-08-14 | 1993-03-02 | Mitsubishi Heavy Ind Ltd | Metal base catalyst and its production |
| JPH07269333A (en) * | 1994-03-31 | 1995-10-17 | Suzuki Motor Corp | Exhaust emission control device for engine and its coating method |
| JPH0971897A (en) * | 1995-09-06 | 1997-03-18 | Akira Fujishima | Aluminum building material and colored aluminum building material having antimicrobial, fungiproof and stainproof properties and their production |
| JPH10296080A (en) * | 1997-04-30 | 1998-11-10 | Hino Motors Ltd | Catalyst for cleaning exhaust gas and catalyst system of combination thereof |
| JP2000178783A (en) * | 1998-12-15 | 2000-06-27 | Nisshin Steel Co Ltd | Galvanized steel sheet with exposed photocatalyst and its production |
| JP2002180272A (en) * | 2000-12-13 | 2002-06-26 | Mitsubishi Alum Co Ltd | Aluminum material having microporous anodic oxide film, and aluminum formed body and fin material |
| JP2003144938A (en) * | 2001-11-12 | 2003-05-20 | Yaskawa Electric Corp | Photocatalyst body and manufacturing method therefor |
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Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5884988A (en) * | 1981-11-12 | 1983-05-21 | Toagosei Chem Ind Co Ltd | Production of catalyst for cathode |
| JPS62114619A (en) * | 1985-11-12 | 1987-05-26 | Cataler Kogyo Kk | Catalyst filter for removing particulate |
| JPH0549945A (en) * | 1991-08-14 | 1993-03-02 | Mitsubishi Heavy Ind Ltd | Metal base catalyst and its production |
| JPH07269333A (en) * | 1994-03-31 | 1995-10-17 | Suzuki Motor Corp | Exhaust emission control device for engine and its coating method |
| JPH0971897A (en) * | 1995-09-06 | 1997-03-18 | Akira Fujishima | Aluminum building material and colored aluminum building material having antimicrobial, fungiproof and stainproof properties and their production |
| JPH10296080A (en) * | 1997-04-30 | 1998-11-10 | Hino Motors Ltd | Catalyst for cleaning exhaust gas and catalyst system of combination thereof |
| JP2000178783A (en) * | 1998-12-15 | 2000-06-27 | Nisshin Steel Co Ltd | Galvanized steel sheet with exposed photocatalyst and its production |
| JP2002180272A (en) * | 2000-12-13 | 2002-06-26 | Mitsubishi Alum Co Ltd | Aluminum material having microporous anodic oxide film, and aluminum formed body and fin material |
| JP2003144938A (en) * | 2001-11-12 | 2003-05-20 | Yaskawa Electric Corp | Photocatalyst body and manufacturing method therefor |
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| JP2005334827A (en) | 2005-12-08 |
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