JP5482646B2 - Aluminum foil with rough surface - Google Patents
Aluminum foil with rough surface Download PDFInfo
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- JP5482646B2 JP5482646B2 JP2010289684A JP2010289684A JP5482646B2 JP 5482646 B2 JP5482646 B2 JP 5482646B2 JP 2010289684 A JP2010289684 A JP 2010289684A JP 2010289684 A JP2010289684 A JP 2010289684A JP 5482646 B2 JP5482646 B2 JP 5482646B2
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- aluminum
- aluminum foil
- rough surface
- plating solution
- film
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- 229910052782 aluminium Inorganic materials 0.000 title claims description 214
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 206
- 239000011888 foil Substances 0.000 title claims description 124
- 238000007747 plating Methods 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- 230000003746 surface roughness Effects 0.000 claims description 26
- -1 aluminum halide Chemical class 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 238000003860 storage Methods 0.000 claims description 20
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical group CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 230000005611 electricity Effects 0.000 claims description 13
- 150000003457 sulfones Chemical class 0.000 claims description 12
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 9
- 239000012433 hydrogen halide Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 67
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000009713 electroplating Methods 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QSVCPXPVEZVSPY-UHFFFAOYSA-N 2-ethyl-1-methyl-1h-imidazol-1-ium;chloride Chemical compound [Cl-].CCC1=[NH+]C=CN1C QSVCPXPVEZVSPY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- HBOOMWHZBIPTMN-UHFFFAOYSA-N 1-hexylsulfonylhexane Chemical compound CCCCCCS(=O)(=O)CCCCCC HBOOMWHZBIPTMN-UHFFFAOYSA-N 0.000 description 1
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 1
- JEXYCADTAFPULN-UHFFFAOYSA-N 1-propylsulfonylpropane Chemical compound CCCS(=O)(=O)CCC JEXYCADTAFPULN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BICAGYDGRXJYGD-UHFFFAOYSA-N hydrobromide;hydrochloride Chemical compound Cl.Br BICAGYDGRXJYGD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- UPOHIXYDQZCJLR-UHFFFAOYSA-J tetraethylazanium tetrafluoride Chemical compound C(C)[N+](CC)(CC)CC.[F-].[F-].[F-].[F-].C(C)[N+](CC)(CC)CC.C(C)[N+](CC)(CC)CC.C(C)[N+](CC)(CC)CC UPOHIXYDQZCJLR-UHFFFAOYSA-J 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Description
本発明は、リチウムイオン二次電池やスーパーキャパシター（電気二重層キャパシター、レドックスキャパシター、リチウムイオンキャパシターなど）といった蓄電デバイスの正極集電体などとして用いることができる、粗面を有するアルミニウム箔に関する。 The present invention relates to an aluminum foil having a rough surface that can be used as a positive electrode current collector of an electricity storage device such as a lithium ion secondary battery or a super capacitor (such as an electric double layer capacitor, a redox capacitor, or a lithium ion capacitor).
携帯電話やノートパソコンなどのモバイルツールの電源に、大きなエネルギー密度を持ち、かつ、放電容量の著しい減少が無いリチウムイオン二次電池が用いられていることは周知の事実であるが、近年、モバイルツールの小型化に伴い、そこに装着されるリチウムイオン二次電池にも小型化の要請がなされている。また、地球温暖化防止対策などの観点からのハイブリッド自動車や太陽光発電などの技術の進展に伴い、電気二重層キャパシター、レドックスキャパシター、リチウムイオンキャパシターなどの大きなエネルギー密度を持つスーパーキャパシターの新しい用途展開が加速しつつあり、これらのさらなる高エネルギー密度化が要求されている。
リチウムイオン二次電池やスーパーキャパシターといった蓄電デバイスは、例えば、電解質としてＬｉＰＦ６やＮＲ４・ＢＦ４（Ｒはアルキル基）などの含フッ素化合物を含んだ有機電解液中に、正極と負極がポリオレフィンなどからなるセパレータを介して配された構造を持つ。正極はＬｉＣｏＯ２（コバルト酸リチウム）や活性炭などの正極活物質と正極集電体からなるとともに、負極はグラファイトや活性炭などの負極活物質と負極集電体からなり、それぞれの形状は集電体の表面に活物質を塗布してシート状に成型したものが一般的である。各電極とも、大きな電圧がかかることに加え、腐食性が高い含フッ素化合物を含んだ有機電解液に浸漬されることから、特に、正極集電体の材料は、電気伝導性に優れるとともに、耐腐食性に優れることが求められる。このような事情から、現在、正極集電体の材料としては、ほぼ１００％に、電気良導体であり、かつ、表面に不働態膜を形成することで優れた耐腐食性を有するアルミニウムが採用されている（負極集電体の材料としては銅やニッケルなどが挙げられる）。
It is a well-known fact that lithium-ion secondary batteries with large energy density and no significant reduction in discharge capacity are used as the power source for mobile tools such as mobile phones and laptop computers. With the downsizing of tools, there is a demand for miniaturization of lithium ion secondary batteries attached to the tools. In addition, with the advancement of technologies such as hybrid vehicles and solar power generation from the viewpoint of global warming prevention measures, new applications of supercapacitors with large energy density such as electric double layer capacitors, redox capacitors and lithium ion capacitors will be developed. Accelerating, and further higher energy density is required.
An electricity storage device such as a lithium ion secondary battery or a supercapacitor has a positive electrode and a negative electrode made of polyolefin in an organic electrolyte containing a fluorine-containing compound such as LiPF 6 or NR 4 .BF 4 (R is an alkyl group) as an electrolyte. It has a structure that is arranged through a separator consisting of. The positive electrode is composed of a positive electrode active material such as LiCoO 2 (lithium cobaltate) and activated carbon and a positive electrode current collector, and the negative electrode is composed of a negative electrode active material such as graphite and activated carbon and a negative electrode current collector, and each shape is a current collector. In general, an active material is applied to the surface of the material and formed into a sheet shape. In addition to applying a large voltage to each electrode, it is immersed in an organic electrolyte containing a highly corrosive fluorine-containing compound, so that the material of the positive electrode current collector is particularly excellent in electrical conductivity and resistance. It is required to be excellent in corrosiveness. Under such circumstances, as the material of the positive electrode current collector, aluminum that is a good electrical conductor and has excellent corrosion resistance by forming a passive film on the surface is adopted as the material of the positive electrode current collector. (Examples of the material for the negative electrode current collector include copper and nickel).
蓄電デバイスの製造において、集電体の表面への活物質の塗布は、高い密着性でもって行う必要があり、また、蓄電デバイスの高エネルギー密度化のためには、可能な限り厚く行うことが望ましい。集電体と活物質の密着性が不十分であると、充放電の際に活物質が自身の体積膨張などによって集電体から剥離するといった問題があるからであり、このような問題は、活物質の塗布を厚くすればするほど発生しやすくなる。とりわけ、近年、ＬｉＣｏＯ２に代わる新たな正極活物質として注目されているＬｉＭｎ２Ｏ４（マンガン酸リチウム）やＬｉＦｅＰＯ４（リン酸鉄リチウム）などは、ＬｉＣｏＯ２よりも粒子径が小さいため、正極集電体として用いるアルミニウム箔に何らの表面処理や表面加工も行わなかった場合、その表面に高い密着性でもって塗布することが困難である。
そこでアルミニウム箔と正極活物質の密着性を高める方法として、アルミニウム箔の表面をエッチングすることによって粗面化する方法が特許文献１において提案されている。しかしながら、この方法には、箔の厚みの均一性を確保することが困難であるといった問題や、エッチングによって箔が痩せ細ることで強度の低下を招くといった問題がある。アルミニウム箔の表面を粗面化する方法としては、アルミニウム箔に対してブラスト処理などを行う方法も考えられるが、正極集電体として用いるアルミニウム箔の厚みは、通常、厚くても５０μｍであるので、このような薄い箔にこうした機械加工を行うと箔が破壊されてしまう恐れが高く、従って採用は困難である。
In the production of an electricity storage device, it is necessary to apply the active material to the surface of the current collector with high adhesion, and in order to increase the energy density of the electricity storage device, it should be as thick as possible. desirable. If the current collector and the active material have insufficient adhesion, there is a problem that the active material peels off from the current collector due to its own volume expansion during charging and discharging. The thicker the active material is applied, the more likely it is. In particular, since LiMn 2 O 4 (lithium manganate), LiFePO 4 (lithium iron phosphate), and the like, which are recently attracting attention as new cathode active materials replacing LiCoO 2 , have a smaller particle diameter than LiCoO 2 , When no surface treatment or surface processing is performed on the aluminum foil used as the current collector, it is difficult to apply the aluminum foil with high adhesion to the surface.
Therefore, as a method for improving the adhesion between the aluminum foil and the positive electrode active material, Patent Document 1 proposes a method of roughening the surface of the aluminum foil by etching. However, this method has a problem that it is difficult to ensure the uniformity of the thickness of the foil, and a problem that the strength is lowered due to thinning and thinning of the foil by etching. As a method for roughening the surface of the aluminum foil, a method of blasting the aluminum foil is also conceivable. However, the thickness of the aluminum foil used as the positive electrode current collector is usually 50 μm at most. If such a thin foil is subjected to such machining, the foil is likely to be destroyed, and therefore, it is difficult to adopt.
そこで本発明は、蓄電デバイスの正極集電体などとして用いることができる、粗面を有するアルミニウム箔を提供することを目的とする。 Then, an object of this invention is to provide the aluminum foil which has a rough surface which can be used as a positive electrode electrical power collector etc. of an electrical storage device.
ところで、本発明者らは、これまでアルミニウムの電気めっき技術について精力的に研究を行ってきている。アルミニウムの電析電位は水素発生の電位よりも卑であるため、水溶液からアルミニウムを電析することは不可能である。従って、電解アルミニウムめっき液は、非水系のもの（溶媒として水を用いないもの）であって、めっき液中に含まれる水分はアルミニウムの析出を阻害する要因となり、均一なアルミニウム被膜を基材の表面に形成することができなくなることから極力排除されるべきものとして取り扱われている。本発明者らは、めっき液中に含まれる水分が均一なアルミニウム被膜の形成に及ぼす悪影響を巧みに利用すれば、表面が粗いアルミニウム被膜を基材の表面に形成することができるのではないかと考え、鋭意検討を重ねた結果、めっき液中に含まれる水分を適量に制御することで、目的を達成することができることを見出した。 By the way, the present inventors have energetically studied the electroplating technology of aluminum so far. Since the electrodeposition potential of aluminum is lower than the potential for hydrogen generation, it is impossible to deposit aluminum from an aqueous solution. Therefore, the electrolytic aluminum plating solution is non-aqueous (no water is used as a solvent), and the moisture contained in the plating solution is a factor that inhibits the precipitation of aluminum, and a uniform aluminum coating is formed on the substrate. Since it cannot be formed on the surface, it is treated as being excluded as much as possible. The inventors of the present invention may be able to form an aluminum coating with a rough surface on the surface of the substrate by skillfully utilizing the adverse effect of moisture contained in the plating solution on the formation of a uniform aluminum coating. As a result of repeated thoughts and intensive studies, it was found that the object can be achieved by controlling the water content in the plating solution to an appropriate amount.
上記の知見に基づいてなされた本発明の粗面を有するアルミニウム箔は、請求項１記載の通り、アルミニウム箔を基材として用い、その表面の少なくとも一部に、含水量が１０〜２０００ｐｐｍの電解アルミニウムめっき液を用いた電解法によってアルミニウム被膜が形成されてなることを特徴とする。
また、請求項２記載の粗面を有するアルミニウム箔は、請求項１記載の粗面を有するアルミニウム箔において、基材として用いるアルミニウム箔が圧延法によって製造されたものであることを特徴とする。
また、請求項３記載の粗面を有するアルミニウム箔は、請求項１または２記載の粗面を有するアルミニウム箔において、電解アルミニウムめっき液が（１）ジアルキルスルホン、（２）アルミニウムハロゲン化物、および、（３）ハロゲン化アンモニウム、第一アミンのハロゲン化水素塩、第二アミンのハロゲン化水素塩、第三アミンのハロゲン化水素塩、一般式：Ｒ１Ｒ２Ｒ３Ｒ４Ｎ・Ｘ（Ｒ１〜Ｒ４は同一または異なってアルキル基、Ｘは第四アンモニウムカチオンに対するカウンターアニオンを示す）で表される第四アンモニウム塩からなる群から選択される少なくとも１つの含窒素化合物を少なくとも含むものであることを特徴とする。
また、請求項４記載の粗面を有するアルミニウム箔は、請求項３記載の粗面を有するアルミニウム箔において、ジアルキルスルホンがジメチルスルホンであることを特徴とする。
また、請求項５記載の粗面を有するアルミニウム箔は、請求項１乃至４のいずれかに記載の粗面を有するアルミニウム箔において、アルミニウム被膜の表面粗さＲａが２．５μｍ以上であることを特徴とする。
また、請求項６記載の粗面を有するアルミニウム箔は、請求項１乃至５のいずれかに記載の粗面を有するアルミニウム箔において、アルミニウム被膜の表面粗さＲａが基材として用いるアルミニウム箔の表面粗さＲａの３倍以上であることを特徴とする。
また、請求項７記載の粗面を有するアルミニウム箔は、請求項１乃至６のいずれかに記載の粗面を有するアルミニウム箔において、アルミニウム被膜の膜厚が１〜５０μｍであることを特徴とする。
また、本発明の蓄電デバイス用正極集電体は、請求項８記載の通り、請求項１乃至７のいずれかに記載の粗面を有するアルミニウム箔からなることを特徴とする。
また、本発明の蓄電デバイス用電極は、請求項９記載の通り、請求項１乃至７のいずれかに記載の粗面を有するアルミニウム箔に電極活物質を担持させてなることを特徴とする。
また、本発明の蓄電デバイスは、請求項１０記載の通り、請求項９記載の蓄電デバイス用電極を用いて構成されてなることを特徴とする。
The aluminum foil having a rough surface according to the present invention made on the basis of the above knowledge uses an aluminum foil as a base material as described in claim 1, and at least a part of the surface of the aluminum foil has an electrolytic content of 10 to 2000 ppm. An aluminum film is formed by an electrolytic method using an aluminum plating solution.
An aluminum foil having a rough surface according to claim 2 is characterized in that, in the aluminum foil having a rough surface according to claim 1, the aluminum foil used as a substrate is produced by a rolling method.
The aluminum foil having a rough surface according to claim 3 is the aluminum foil having a rough surface according to claim 1 or 2, wherein the electrolytic aluminum plating solution is (1) dialkyl sulfone, (2) aluminum halide, and (3) Ammonium halide, hydrogen halide salt of primary amine, hydrogen halide salt of secondary amine, hydrogen halide salt of tertiary amine, general formula: R 1 R 2 R 3 R 4 N · X (R 1 to R 4 are the same or different and each contains at least one nitrogen-containing compound selected from the group consisting of a quaternary ammonium salt represented by an alkyl group, and X represents a counter anion for a quaternary ammonium cation). It is characterized by.
The aluminum foil having a rough surface according to claim 4 is the aluminum foil having a rough surface according to claim 3, wherein the dialkyl sulfone is dimethyl sulfone.
The aluminum foil having a rough surface according to claim 5 is the aluminum foil having a rough surface according to any one of claims 1 to 4, wherein the surface roughness Ra of the aluminum film is 2.5 μm or more. Features.
The aluminum foil having a rough surface according to claim 6 is the aluminum foil having the rough surface according to any one of claims 1 to 5, wherein the surface roughness Ra of the aluminum coating is used as a substrate. It is characterized by being at least three times the roughness Ra.
The aluminum foil having a rough surface according to claim 7 is the aluminum foil having a rough surface according to any one of claims 1 to 6, wherein the film thickness of the aluminum coating is 1 to 50 µm. .
Moreover, the positive electrode electrical power collector for electrical storage devices of this invention consists of the aluminum foil which has the rough surface in any one of Claims 1 thru | or 7, as described in Claim 8.
In addition, an electrode for an electricity storage device of the present invention is characterized in that, as described in claim 9, an electrode active material is supported on the aluminum foil having a rough surface according to any one of claims 1 to 7.
Moreover, the electrical storage device of this invention is comprised using the electrode for electrical storage devices of Claim 9 as described in Claim 10.
本発明によれば、蓄電デバイスの正極集電体などとして用いることができる、粗面を有するアルミニウム箔を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the aluminum foil which has a rough surface which can be used as a positive electrode electrical power collector etc. of an electrical storage device can be provided.
本発明の粗面を有するアルミニウム箔は、アルミニウム箔を基材として用い、その表面の少なくとも一部に、含水量が１０〜２０００ｐｐｍの電解アルミニウムめっき液を用いた電解法によってアルミニウム被膜が形成されてなることを特徴とするものである。即ち、本発明の粗面を有するアルミニウム箔は、非水系のめっき液中に含まれる適量の水分を利用して、意図して表面が粗いアルミニウム被膜を基材としてのアルミニウム箔の表面に形成することで得られるものである。 The aluminum foil having a rough surface of the present invention uses an aluminum foil as a base material, and an aluminum coating is formed on at least a part of the surface by an electrolytic method using an electrolytic aluminum plating solution having a water content of 10 to 2000 ppm. It is characterized by. That is, the aluminum foil having a rough surface of the present invention intentionally forms an aluminum film having a rough surface on the surface of the aluminum foil as a base material by utilizing an appropriate amount of moisture contained in the non-aqueous plating solution. It can be obtained.
本発明において基材として用いるアルミニウム箔は、例えば圧延法によって製造された市販のものであってよいが、電解法によって製造されたものでもよい。電解法によるアルミニウム箔の製造は、例えば電解アルミニウムめっき液を用いた電解法によって所定の基材の表面にアルミニウム被膜を形成した後、当該被膜を基材から剥離して行うことができる。アルミニウム箔の厚みは、例えば５〜５０μｍであってよい。 The aluminum foil used as a base material in the present invention may be a commercially available product manufactured by, for example, a rolling method, or may be manufactured by an electrolytic method. The production of an aluminum foil by an electrolytic method can be performed by, for example, forming an aluminum film on the surface of a predetermined substrate by an electrolytic method using an electrolytic aluminum plating solution, and then peeling the film from the substrate. The thickness of the aluminum foil may be 5 to 50 μm, for example.
基材としてのアルミニウム箔の表面に形成するアルミニウム被膜は、例えば、表面粗さＲａが２．５μｍ以上、および／または、表面粗さＲａがアルミニウム被膜を表面に形成するアルミニウム箔のＲａの３倍以上の凹凸を表面に有する被膜であり、デンドライト状に結晶成長した被膜や、無数の陥没を伴って結晶成長した被膜などであってよい。こうした表面が粗いアルミニウム被膜は、めっき液中に含まれる水分がアルミニウム被膜の形成過程における均一な結晶成長を阻害することによって形成されるものであり、一般的には回避されるべきものであるが、本発明において意図するものである。めっき液の含水量を１０〜２０００ｐｐｍと規定するのは、含水量が１０ｐｐｍを下回ると、めっき液中に含まれる水分が少なすぎて、アルミニウム被膜の形成過程における均一な結晶成長を阻害しないことによって表面が平坦（例えばＲａが２．５μｍ未満）なアルミニウム被膜が形成される恐れがある一方、含水量が２０００ｐｐｍを超えると、めっき液中に含まれる水分が多すぎて、形成されるアルミニウム被膜が不純物を多量に含んでしまう現象や、被膜が黒ずんでしまう現象（焼けと呼ばれる現象）が発生する恐れがあるからである。なお、めっき液の含水量の調整方法は特段限定されるものではなく、めっき液に対して所定量の水を添加することによって行ってもよいし、めっき液の構成成分となる物質が水和物である場合には、当該物質が保持する水分子を利用して行ってもよい。また、これらの方法を組み合わせて行ってもよい。 The aluminum film formed on the surface of the aluminum foil as the base material has, for example, a surface roughness Ra of 2.5 μm or more and / or a surface roughness Ra that is three times the Ra of the aluminum foil that forms the aluminum film on the surface. It is a film having the above irregularities on the surface, and may be a film that has been crystal-grown in a dendrite shape, or a film that has been crystal-grown with numerous depressions. Such a rough aluminum film is formed by the moisture contained in the plating solution being hindered from uniform crystal growth in the process of forming the aluminum film, and should generally be avoided. This is intended in the present invention. The reason why the water content of the plating solution is defined as 10 to 2000 ppm is that when the water content is less than 10 ppm, the water contained in the plating solution is too small and does not inhibit the uniform crystal growth in the formation process of the aluminum coating. On the other hand, an aluminum film having a flat surface (for example, Ra of less than 2.5 μm) may be formed. On the other hand, if the water content exceeds 2000 ppm, the plating solution contains too much water, and the formed aluminum film This is because there is a possibility that a phenomenon of containing a large amount of impurities or a phenomenon of darkening the film (a phenomenon called burning) may occur. The method for adjusting the water content of the plating solution is not particularly limited, and it may be performed by adding a predetermined amount of water to the plating solution, or the substance that constitutes the plating solution may be hydrated. In the case of a product, water molecules held by the material may be used. Moreover, you may carry out combining these methods.
本発明の粗面を有するアルミニウム箔を蓄電デバイス用正極集電体として用いることを想定した場合、基材として用いるアルミニウム箔の表面に形成する表面が粗いアルミニウム被膜の膜厚は、例えば１〜５０μｍが望ましいが、基材として用いるアルミニウム箔の厚みと合わせた粗面を有するアルミニウム箔の厚みが５０μｍ以下となる膜厚がより望ましく、３０μｍ以下となる膜厚がさらに望ましい。膜厚が１μｍを下回ると十分な凹凸が形成されない恐れがある一方、膜厚が５０μｍを超えるといったん凹凸が形成されてもさらなる結晶成長によって凹凸が消失する方向に進む恐れがある。なお、表面が粗いアルミニウム被膜は、基材として用いるアルミニウム箔の表面全体を被覆するように形成される必要は必ずしもなく、箔の表面に被膜が形成されない部分があってもよい。また、ピンホールを有するものであってもよい。被膜が形成されない部分や被膜にピンホールが存在しても、アルミニウム箔を基材として用いているので、有機電解液中において安定に存在し、電池特性に悪影響を及ぼすことはない（アルミニウム箔を基材として用いるのはこの理由による）。 When it is assumed that the aluminum foil having a rough surface of the present invention is used as a positive electrode current collector for an electricity storage device, the film thickness of the rough aluminum film formed on the surface of the aluminum foil used as the substrate is, for example, 1 to 50 μm. However, the thickness of the aluminum foil having a rough surface combined with the thickness of the aluminum foil used as the base material is more preferably 50 μm or less, and more preferably 30 μm or less. If the film thickness is less than 1 μm, sufficient unevenness may not be formed. On the other hand, if the film thickness exceeds 50 μm, even if the unevenness is once formed, the unevenness may disappear due to further crystal growth. The aluminum film having a rough surface is not necessarily formed so as to cover the entire surface of the aluminum foil used as the base material, and there may be a portion where the film is not formed on the surface of the foil. Moreover, you may have a pinhole. Even if there are pinholes in the part where the film is not formed or in the film, since the aluminum foil is used as the base material, it is stably present in the organic electrolyte and does not adversely affect the battery characteristics (the aluminum foil This is why it is used as a base material).
本発明において用いる電解アルミニウムめっき液は、めっき液中に適量の水分を含むことで、電解法によってアルミニウム箔の表面に表面が粗いアルミニウム被膜を形成することができるものであれば特段限定されるものではなく、例えば塩化アルミニウムとエチルメチルイミダゾリウムクロリドからなるめっき液をはじめとする公知のものであってよい。しかしながら、好適な電解アルミニウムめっき液としては、本発明者らが開発した、（１）ジアルキルスルホン、（２）アルミニウムハロゲン化物、および、（３）ハロゲン化アンモニウム、第一アミンのハロゲン化水素塩、第二アミンのハロゲン化水素塩、第三アミンのハロゲン化水素塩、一般式：Ｒ１Ｒ２Ｒ３Ｒ４Ｎ・Ｘ（Ｒ１〜Ｒ４は同一または異なってアルキル基、Ｘは第四アンモニウムカチオンに対するカウンターアニオンを示す）で表される第四アンモニウム塩からなる群から選択される少なくとも１つの含窒素化合物を少なくとも含むものが挙げられる。このめっき液を用いれば、速い成膜速度で延性に富む高純度のアルミニウム被膜を基材としてのアルミニウム箔の表面に形成することができる。 The electrolytic aluminum plating solution used in the present invention is particularly limited as long as it contains an appropriate amount of moisture in the plating solution and can form an aluminum film having a rough surface on the surface of the aluminum foil by an electrolytic method. Instead, it may be a known one including, for example, a plating solution made of aluminum chloride and ethylmethylimidazolium chloride. However, as a suitable electrolytic aluminum plating solution, the present inventors have developed (1) dialkyl sulfone, (2) aluminum halide, and (3) ammonium halide, a primary amine hydrogen halide salt, Secondary amine hydrogen halide salt, tertiary amine hydrogen halide salt, general formula: R 1 R 2 R 3 R 4 N · X (R 1 to R 4 are the same or different and are alkyl groups, X is the fourth And a compound containing at least one nitrogen-containing compound selected from the group consisting of quaternary ammonium salts represented by: By using this plating solution, it is possible to form a high-purity aluminum coating rich in ductility at a high film formation rate on the surface of an aluminum foil as a substrate.
上記の電解アルミニウムめっき液に含ませるジアルキルスルホンとしては、ジメチルスルホン、ジエチルスルホン、ジプロピルスルホン、ジヘキシルスルホン、メチルエチルスルホンなどのアルキル基の炭素数が１〜６のもの（直鎖状でも分岐状でもよい）を例示することができるが、良好な電気伝導性や入手の容易性などの観点からはジメチルスルホンを好適に採用することができる。 Examples of the dialkyl sulfone contained in the above electrolytic aluminum plating solution include those having 1 to 6 carbon atoms in the alkyl group such as dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dihexyl sulfone, and methylethyl sulfone (both linear and branched). However, dimethyl sulfone can be preferably employed from the viewpoint of good electrical conductivity and availability.
アルミニウムハロゲン化物としては、塩化アルミニウムや臭化アルミニウムなどを例示することができる。一般的には、アルミニウムの析出を阻害する要因となるめっき液に含まれる水分の量を可能な限り少なくするという観点から、用いるアルミニウムハロゲン化物は無水物であることが望ましいが、本発明においては水和物を用いることで、当該物質が保持する水分子をめっき液に含まれる水分として利用してもよい。 Examples of the aluminum halide include aluminum chloride and aluminum bromide. In general, from the viewpoint of minimizing the amount of moisture contained in the plating solution, which is a factor that hinders the precipitation of aluminum, the aluminum halide used is preferably an anhydride, but in the present invention, By using a hydrate, water molecules held by the substance may be used as moisture contained in the plating solution.
含窒素化合物として採用することができるハロゲン化アンモニウムとしては、塩化アンモニウムや臭化アンモニウムなどを例示することができる。また、第一アミン〜第三アミンとしては、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、プロピルアミン、ジプロピルアミン、トリプロピルアミン、ヘキシルアミン、メチルエチルアミンなどのアルキル基の炭素数が１〜６のもの（直鎖状でも分岐状でもよい）を例示することができる。ハロゲン化水素としては、塩化水素や臭化水素などを例示することができる。一般式：Ｒ１Ｒ２Ｒ３Ｒ４Ｎ・Ｘ（Ｒ１〜Ｒ４は同一または異なってアルキル基、Ｘは第四アンモニウムカチオンに対するカウンターアニオンを示す）で表される第四アンモニウム塩におけるＲ１〜Ｒ４で示されるアルキル基としては、メチル基、エチル基、プロピル基、ヘキシル基などの炭素数が１〜６のもの（直鎖状でも分岐状でもよい）を例示することができる。Ｘとしては塩素イオンや臭素イオンやヨウ素イオンなどのハロゲン化物イオンの他、ＢＦ４ −やＰＦ６ −などを例示することができる。具体的な化合物としては、塩化テトラメチルアンモニウム、臭化テトラメチルアンモニウム、ヨウ化テトラメチルアンモニウム、四フッ化ホウ素テトラエチルアンモニウムなどを例示することができる。好適な含窒素化合物としては、速い成膜速度で延性に富む高純度のアルミニウム被膜の形成を容易にする点において第三アミンの塩酸塩、例えばトリメチルアミン塩酸塩を挙げることができる。 Examples of the ammonium halide that can be employed as the nitrogen-containing compound include ammonium chloride and ammonium bromide. In addition, as primary amine to tertiary amine, the carbon number of alkyl groups such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, hexylamine, methylethylamine, etc. 1 to 6 (which may be linear or branched) can be exemplified. Examples of the hydrogen halide include hydrogen chloride and hydrogen bromide. R in a quaternary ammonium salt represented by the general formula: R 1 R 2 R 3 R 4 N · X (R 1 to R 4 are the same or different and are an alkyl group, X represents a counter anion for a quaternary ammonium cation) Examples of the alkyl group represented by 1 to R 4 include those having 1 to 6 carbon atoms (which may be linear or branched) such as a methyl group, an ethyl group, a propyl group, and a hexyl group. Examples of X include halide ions such as chlorine ions, bromine ions and iodine ions, as well as BF 4 − and PF 6 − . Specific examples of the compound include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, and tetraethylammonium tetrafluoride. Suitable nitrogen-containing compounds include tertiary amine hydrochlorides, such as trimethylamine hydrochloride, in terms of facilitating the formation of a high-purity aluminum film having high ductility at a high film formation rate.
ジアルキルスルホン、アルミニウムハロゲン化物、含窒素化合物の配合割合は、例えば、ジアルキルスルホン１０モルに対し、アルミニウムハロゲン化物は１．５〜４．０モルが望ましく、２．０〜３．５モルがより望ましい。含窒素化合物は０．０１〜２．０モルが望ましく、０．０５〜１．５モルがより望ましい。アルミニウムハロゲン化物の配合量がジアルキルスルホン１０モルに対し１．５モルを下回ると形成されるアルミニウム被膜が黒ずんでしまう現象（焼けと呼ばれる現象）が発生する恐れや成膜効率が低下する恐れがある一方、４．０モルを超えるとめっき液の液抵抗が高くなりすぎることでめっき液が発熱して分解する恐れがある。また、含窒素化合物の配合量がジアルキルスルホン１０モルに対し０．０１モルを下回ると配合することの効果、即ち、めっき液の電気伝導性の改善に基づく高電流密度印加でのめっき処理の実現による成膜速度の向上、アルミニウム被膜の高純度化や延性の向上などの効果が得られにくくなる恐れがある一方、２．０モルを超えるとめっき液の組成が本質的に変わってしまうことでアルミニウムが析出しなくなってしまう恐れがある。 The blending ratio of the dialkyl sulfone, the aluminum halide, and the nitrogen-containing compound is, for example, preferably 1.5 to 4.0 mol, more preferably 2.0 to 3.5 mol for the aluminum halide with respect to 10 mol of the dialkyl sulfone. . The nitrogen-containing compound is preferably 0.01 to 2.0 mol, more preferably 0.05 to 1.5 mol. If the blending amount of aluminum halide is less than 1.5 moles relative to 10 moles of dialkyl sulfone, the formed aluminum film may be darkened (a phenomenon called burning), or the film formation efficiency may be lowered. On the other hand, if it exceeds 4.0 moles, the plating solution may become too hot and decompose due to excessively high resistance of the plating solution. In addition, the effect of blending when the compounding amount of the nitrogen-containing compound is less than 0.01 mole with respect to 10 moles of dialkyl sulfone, that is, the realization of plating treatment with high current density application based on the improvement of the electrical conductivity of the plating solution While there is a risk that the effects of improving the film formation rate due to the increase in purity, improving the purity of the aluminum coating, and improving the ductility may be difficult to obtain, the composition of the plating solution will change essentially when it exceeds 2.0 moles. There is a risk that aluminum will not precipitate.
上記の電解アルミニウムめっき液を用いためっき処理は、例えば、めっき液の温度が８０〜１１０℃、印加電流密度が０．０５〜２０Ａ／ｄｍ２の条件下、基材としてのアルミニウム箔を陰極として行えばよい（陽極の材質としては例えばアルミニウムを例示することができる）。めっき液の温度の下限はめっき液の融点を考慮して決定されるべきものであり、望ましくは８５℃、より望ましくは９５℃である（めっき液の融点を下回るとめっき液が固化するのでめっき処理がもはや行えなくなる）。一方、めっき液の温度が１１０℃を超えると基材としてのアルミニウム箔の表面に形成されたアルミニウム被膜とめっき液の間での反応が活発化し、アルミニウム被膜中に不純物が多く取り込まれることでその純度が低下する恐れがある。また、印加電流密度が０．０５Ａ／ｄｍ２を下回ると成膜効率が低下する恐れがある一方、２０Ａ／ｄｍ２を超えると含窒素化合物の分解などが原因で安定なめっき処理が行えなくなったり延性に富む高純度のアルミニウム被膜が得られなくなったりする恐れがある。上記の電解アルミニウムめっき液の特筆すべき利点は、１０Ａ／ｄｍ２以上の電流密度を印加しても安定なめっき処理が可能なため、成膜速度の向上を図ることができる点にある。なお、めっき処理の時間は、アルミニウム被膜の所望する膜厚、めっき液の温度や印加電流密度などにも依存するが、通常、１〜９０分間である（生産効率を考慮すると１〜６０分間が望ましい）。 The plating treatment using the above electrolytic aluminum plating solution is performed using, for example, an aluminum foil as a base material as a cathode under conditions where the temperature of the plating solution is 80 to 110 ° C. and the applied current density is 0.05 to 20 A / dm 2. (Aluminum can be exemplified as the material of the anode). The lower limit of the temperature of the plating solution should be determined in consideration of the melting point of the plating solution, preferably 85 ° C., more preferably 95 ° C. (Because the plating solution is solidified below the melting point of the plating solution, plating is performed. Processing is no longer possible). On the other hand, when the temperature of the plating solution exceeds 110 ° C., the reaction between the aluminum coating formed on the surface of the aluminum foil as the substrate and the plating solution is activated, and a large amount of impurities are taken into the aluminum coating. There is a risk that the purity may decrease. On the other hand, when the applied current density is less than 0.05 A / dm 2 , the film formation efficiency may be reduced. On the other hand, when the applied current density is more than 20 A / dm 2 , stable plating may not be performed due to decomposition of nitrogen-containing compounds. There is a possibility that a high-purity aluminum coating rich in ductility cannot be obtained. A notable advantage of the electrolytic aluminum plating solution is that the deposition rate can be improved because stable plating can be performed even when a current density of 10 A / dm 2 or more is applied. The time for the plating treatment depends on the desired film thickness of the aluminum coating, the temperature of the plating solution, the applied current density, and the like, but is usually 1 to 90 minutes (1 to 60 minutes is considered in consideration of production efficiency). desirable).
以上のようにして製造される本発明の粗面を有するアルミニウム箔は、例えば蓄電デバイスの製造において、基材として用いたアルミニウム箔の表面に形成したアルミニウム被膜の表面の凹凸を利用して、正極活物質を高い密着性でもって塗布することができるので、正極集電体として有用である。 The aluminum foil having the rough surface of the present invention produced as described above is a positive electrode utilizing unevenness on the surface of the aluminum film formed on the surface of the aluminum foil used as a base material in the production of an electricity storage device, for example. Since the active material can be applied with high adhesion, it is useful as a positive electrode current collector.
以下、本発明を実施例によって詳細に説明するが、本発明は以下の記載に限定して解釈されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is limited to the following description and is not interpreted.
参考例１：
以下の実施例と比較例においてアルミニウム被膜を形成するための基材として用いた、厚みが１５μｍの市販の圧延アルミニウム箔（日本製箔社製）の表面写真を図１に示す。この圧延アルミニウム箔の表面粗さＲａを測定したところ、０．８μｍであった（ＫＥＹＥＮＣＥ社製の超深度形状測定顕微鏡：ＶＫ−８５１０を用いて測定、以下同じ）。
Reference example 1:
A surface photograph of a commercially available rolled aluminum foil (manufactured by Nippon Foil Co., Ltd.) having a thickness of 15 μm used as a base material for forming an aluminum coating in the following Examples and Comparative Examples is shown in FIG. The surface roughness Ra of the rolled aluminum foil was measured and found to be 0.8 μm (measured using an ultra-deep shape measuring microscope manufactured by KEYENCE, Inc .: VK-8510, the same applies hereinafter).
実施例１：
ジメチルスルホン：塩化アルミニウム：トリメチルアミン塩酸塩をモル比で１０：３：０．０１の割合で混合し、１１０℃で溶解させて電解アルミニウムめっき液を調製した。この際、めっき液に水を添加してその含水量を３００ｐｐｍに調整した（めっき液の含水量は三菱化学社製の微量水分測定装置：ＣＡ−１００を用いて測定、以下同じ）。この含水めっき液を用いて、陽極に純度９９．９９ｍａｓｓ％のアルミニウム板、陰極に厚みが１５μｍの圧延アルミニウム箔を用い、１．５Ａ／ｄｍ２の印加電流密度で、めっき液を９５℃に保って３００ｒｐｍの攪拌速度で攪拌しながら電気めっき処理を６０分間行い、圧延アルミニウム箔の表面全体にアルミニウム被膜を形成した。こうして圧延アルミニウム箔の表面に形成されたアルミニウム被膜は、デンドライト状に結晶成長した膜厚が約１５μｍの被膜であり（表面写真を図２に示す）、表面粗さＲａは１３．４μｍであった（基材として用いたアルミニウム箔の表面粗さＲａの１６．８倍）。よって、この方法によれば、粗面を有するアルミニウム箔を得ることができることがわかった。
Example 1:
Dimethylsulfone: aluminum chloride: trimethylamine hydrochloride was mixed at a molar ratio of 10: 3: 0.01 and dissolved at 110 ° C. to prepare an electrolytic aluminum plating solution. At this time, water was added to the plating solution to adjust its water content to 300 ppm (the water content of the plating solution was measured using a trace moisture measuring device: CA-100 manufactured by Mitsubishi Chemical Corporation, the same applies hereinafter). Using this hydrous plating solution, an aluminum plate having a purity of 99.99 mass% is used for the anode, a rolled aluminum foil having a thickness of 15 μm is used for the cathode, and the plating solution is kept at 95 ° C. at an applied current density of 1.5 A / dm 2. Then, electroplating was performed for 60 minutes while stirring at a stirring speed of 300 rpm, and an aluminum film was formed on the entire surface of the rolled aluminum foil. The aluminum film thus formed on the surface of the rolled aluminum foil was a film having a film thickness of about 15 μm that was crystal-grown in a dendritic form (a surface photograph is shown in FIG. 2), and the surface roughness Ra was 13.4 μm. (16.8 times the surface roughness Ra of the aluminum foil used as the substrate). Therefore, according to this method, it turned out that the aluminum foil which has a rough surface can be obtained.
実施例２：
ジメチルスルホン：塩化アルミニウム：トリメチルアミン塩酸塩をモル比で１０：３：１．５の割合で混合し、１１０℃で溶解させて電解アルミニウムめっき液を調製した。この際、めっき液に水を添加してその含水量を５００ｐｐｍに調整した。この含水めっき液を用いて、陽極に純度９９．９９ｍａｓｓ％のアルミニウム板、陰極に厚みが１５μｍの圧延アルミニウム箔を用い、３Ａ／ｄｍ２の印加電流密度で、めっき液を９５℃に保って３００ｒｐｍの攪拌速度で攪拌しながら電気めっき処理を１０分間行い、圧延アルミニウム箔の表面全体にアルミニウム被膜を形成した。こうして圧延アルミニウム箔の表面に形成されたアルミニウム被膜は、デンドライト状に結晶成長した膜厚が約５μｍの被膜であり、表面粗さＲａは４．４μｍであった（基材として用いたアルミニウム箔の表面粗さＲａの５．５倍）。よって、この方法によれば、粗面を有するアルミニウム箔を得ることができることがわかった。
Example 2:
Dimethylsulfone: aluminum chloride: trimethylamine hydrochloride was mixed at a molar ratio of 10: 3: 1.5 and dissolved at 110 ° C. to prepare an electrolytic aluminum plating solution. At this time, water was added to the plating solution to adjust its water content to 500 ppm. Using this hydrous plating solution, an aluminum plate having a purity of 99.99 mass% is used as the anode, a rolled aluminum foil having a thickness of 15 μm is used as the cathode, and the plating solution is kept at 95 ° C. at an applied current density of 3 A / dm 2 and 300 rpm. The electroplating treatment was performed for 10 minutes while stirring at a stirring speed of 1 to form an aluminum coating on the entire surface of the rolled aluminum foil. The aluminum film thus formed on the surface of the rolled aluminum foil was a film having a dendritic crystal growth of about 5 μm and a surface roughness Ra of 4.4 μm (of the aluminum foil used as the substrate). 5.5 times the surface roughness Ra). Therefore, according to this method, it turned out that the aluminum foil which has a rough surface can be obtained.
実施例３：
ジメチルスルホン：塩化アルミニウム：トリメチルアミン塩酸塩をモル比で１０：３：０．５の割合で混合し、１１０℃で溶解させて電解アルミニウムめっき液を調製した。この際、めっき液に水を添加してその含水量を２０ｐｐｍに調整した。この含水めっき液を用いて、陽極に純度９９．９９ｍａｓｓ％のアルミニウム板、陰極に厚みが１５μｍの圧延アルミニウム箔を用い、０．１Ａ／ｄｍ２の印加電流密度で、めっき液を９５℃に保って３００ｒｐｍの攪拌速度で攪拌しながら電気めっき処理を５０分間行い、圧延アルミニウム箔の表面全体にアルミニウム被膜を形成した。こうして圧延アルミニウム箔の表面に形成されたアルミニウム被膜は、デンドライト状に結晶成長した膜厚が約２μｍの被膜であり、表面粗さＲａは２．８μｍであった（基材として用いたアルミニウム箔の表面粗さＲａの３．５倍）。よって、この方法によれば、粗面を有するアルミニウム箔を得ることができることがわかった。
Example 3:
Dimethylsulfone: aluminum chloride: trimethylamine hydrochloride was mixed at a molar ratio of 10: 3: 0.5 and dissolved at 110 ° C. to prepare an electrolytic aluminum plating solution. At this time, water was added to the plating solution to adjust its water content to 20 ppm. Using this hydrous plating solution, an aluminum plate having a purity of 99.99 mass% is used for the anode, a rolled aluminum foil having a thickness of 15 μm is used for the cathode, and the plating solution is kept at 95 ° C. at an applied current density of 0.1 A / dm 2. Then, electroplating was performed for 50 minutes while stirring at a stirring speed of 300 rpm to form an aluminum coating on the entire surface of the rolled aluminum foil. The aluminum film thus formed on the surface of the rolled aluminum foil was a film having a dendritic crystal growth of about 2 μm and a surface roughness Ra of 2.8 μm (the aluminum foil used as the base material). (Surface roughness Ra is 3.5 times). Therefore, according to this method, it turned out that the aluminum foil which has a rough surface can be obtained.
実施例４：
ジメチルスルホン：塩化アルミニウム：トリメチルアミン塩酸塩をモル比で１０：３：０．０１の割合で混合し、１１０℃で溶解させて電解アルミニウムめっき液を調製した。この際、めっき液に水を添加してその含水量を２０００ｐｐｍに調整した。この含水めっき液を用いて、陽極に純度９９．９９ｍａｓｓ％のアルミニウム板、陰極に厚みが１５μｍの圧延アルミニウム箔を用い、５Ａ／ｄｍ２の印加電流密度で、めっき液を９５℃に保って３００ｒｐｍの攪拌速度で攪拌しながら電気めっき処理を１５分間行い、圧延アルミニウム箔の表面全体にアルミニウム被膜を形成した。こうして圧延アルミニウム箔の表面に形成されたアルミニウム被膜は、無数の陥没を伴って結晶成長した膜厚が約１５μｍの被膜であり（表面写真を図３に示す。陥没はめっき液に含まれる水分の分解によって発生した気泡の跡でありそのほとんどの最深部にピンホールが認められる）、表面粗さＲａは１０．８μｍであった（基材として用いたアルミニウム箔の表面粗さＲａの１３．５倍）。よって、この方法によれば、粗面を有するアルミニウム箔を得ることができることがわかった。
Example 4:
Dimethylsulfone: aluminum chloride: trimethylamine hydrochloride was mixed at a molar ratio of 10: 3: 0.01 and dissolved at 110 ° C. to prepare an electrolytic aluminum plating solution. At this time, water was added to the plating solution to adjust the water content to 2000 ppm. Using this water-containing plating solution, an aluminum plate having a purity of 99.99 mass% is used as the anode, a rolled aluminum foil having a thickness of 15 μm is used as the cathode, and the plating solution is maintained at 95 ° C. at an applied current density of 5 A / dm 2 and 300 rpm. The electroplating process was performed for 15 minutes while stirring at a stirring speed of 1 to form an aluminum coating on the entire surface of the rolled aluminum foil. The aluminum film thus formed on the surface of the rolled aluminum foil is a film having a film thickness of about 15 μm which has been crystal-grown with innumerable depressions (surface photograph is shown in FIG. 3. The depressions represent the moisture contained in the plating solution. The surface roughness Ra was 10.8 μm (13.5 of the surface roughness Ra of the aluminum foil used as the base material). Times). Therefore, according to this method, it turned out that the aluminum foil which has a rough surface can be obtained.
実施例５：
ジメチルスルホン：塩化アルミニウム：トリメチルアミン塩酸塩をモル比で１０：３：０．０５の割合で混合し、１１０℃で溶解させて電解アルミニウムめっき液を調製した。この際、めっき液に水を添加してその含水量を１０００ｐｐｍに調整した。この含水めっき液を用いて、陽極に純度９９．９９ｍａｓｓ％のアルミニウム板、陰極に厚みが１５μｍの圧延アルミニウム箔を用い、２０Ａ／ｄｍ２の印加電流密度で、めっき液を９５℃に保って３００ｒｐｍの攪拌速度で攪拌しながら電気めっき処理を１分間行い、圧延アルミニウム箔の表面全体にアルミニウム被膜を形成した。こうして圧延アルミニウム箔の表面に形成されたアルミニウム被膜は、無数の陥没を伴って結晶成長した膜厚が約４μｍの被膜であり、表面粗さＲａは３．１μｍであった（基材として用いたアルミニウム箔の表面粗さＲａの３．９倍）。よって、この方法によれば、粗面を有するアルミニウム箔を得ることができることがわかった。
Example 5:
Dimethylsulfone: aluminum chloride: trimethylamine hydrochloride was mixed at a molar ratio of 10: 3: 0.05 and dissolved at 110 ° C. to prepare an electrolytic aluminum plating solution. At this time, water was added to the plating solution to adjust its water content to 1000 ppm. Using this hydrous plating solution, an aluminum plate having a purity of 99.99 mass% was used as the anode, a rolled aluminum foil having a thickness of 15 μm was used as the cathode, and the plating solution was kept at 95 ° C. and 300 rpm with an applied current density of 20 A / dm 2. The electroplating treatment was performed for 1 minute while stirring at a stirring speed of 1 to form an aluminum coating on the entire surface of the rolled aluminum foil. The aluminum film thus formed on the surface of the rolled aluminum foil was a film having a film thickness of about 4 μm, which had been crystal-grown with numerous depressions, and had a surface roughness Ra of 3.1 μm (used as a substrate). (3.9 times the surface roughness Ra of the aluminum foil). Therefore, according to this method, it turned out that the aluminum foil which has a rough surface can be obtained.
実施例６：
８Ａ／ｄｍ２の印加電流密度で電気めっき処理を３０分間行うこと以外は実施例４と同様にして、圧延アルミニウム箔の表面全体にアルミニウム被膜を形成した。こうして圧延アルミニウム箔の表面に形成されたアルミニウム被膜は、無数の陥没を伴って結晶成長した膜厚が約４８μｍの被膜であり、表面粗さＲａは１４．８μｍであった（基材として用いたアルミニウム箔の表面粗さＲａの１１．８倍）。よって、この方法によれば、粗面を有するアルミニウム箔を得ることができることがわかった。
Example 6:
An aluminum coating was formed on the entire surface of the rolled aluminum foil in the same manner as in Example 4 except that the electroplating treatment was performed at an applied current density of 8 A / dm 2 for 30 minutes. The aluminum film thus formed on the surface of the rolled aluminum foil was a film having a film thickness of about 48 μm grown with numerous depressions and a surface roughness Ra of 14.8 μm (used as a substrate). 11.8 times the surface roughness Ra of the aluminum foil). Therefore, according to this method, it turned out that the aluminum foil which has a rough surface can be obtained.
実施例７：
塩化アルミニウム：エチルメチルイミダゾリウムクロリドをモル比で６７：３３の割合で混合し、８０℃で溶解させて電解アルミニウムめっき液を調製した。この際、めっき液に水を添加してその含水量を５００ｐｐｍに調整した。この含水めっき液を用いて、陽極に純度９９．９９ｍａｓｓ％のアルミニウム板、陰極に厚みが１５μｍの圧延アルミニウム箔を用い、１．５Ａ／ｄｍ２の印加電流密度で、めっき液を９５℃に保って３００ｒｐｍの攪拌速度で攪拌しながら電気めっき処理を６０分間行い、圧延アルミニウム箔の表面全体にアルミニウム被膜を形成した。こうして圧延アルミニウム箔の表面に形成されたアルミニウム被膜は、デンドライト状に結晶成長した膜厚が約１５μｍの被膜であり、表面粗さＲａは１０．４μｍであった（基材として用いたアルミニウム箔の表面粗さＲａの１３倍）。よって、この方法によれば、粗面を有するアルミニウム箔を得ることができることがわかった。
Example 7:
Aluminum chloride: ethylmethylimidazolium chloride was mixed at a molar ratio of 67:33 and dissolved at 80 ° C. to prepare an electrolytic aluminum plating solution. At this time, water was added to the plating solution to adjust its water content to 500 ppm. Using this hydrous plating solution, an aluminum plate having a purity of 99.99 mass% is used for the anode, a rolled aluminum foil having a thickness of 15 μm is used for the cathode, and the plating solution is kept at 95 ° C. at an applied current density of 1.5 A / dm 2. Then, electroplating was performed for 60 minutes while stirring at a stirring speed of 300 rpm, and an aluminum film was formed on the entire surface of the rolled aluminum foil. The aluminum film thus formed on the surface of the rolled aluminum foil was a film having a film thickness of about 15 μm that was crystal-grown in a dendrite shape, and the surface roughness Ra was 10.4 μm (the aluminum film used as the base material). 13 times the surface roughness Ra). Therefore, according to this method, it turned out that the aluminum foil which has a rough surface can be obtained.
比較例１：
めっき液の含水量を４ｐｐｍに調整すること以外は実施例１と同様にして、圧延アルミニウム箔の表面全体に膜厚が約１５μｍのアルミニウム被膜を形成した。こうして圧延アルミニウム箔の表面に形成されたアルミニウム被膜の表面粗さＲａは１．１μｍであった（基材として用いたアルミニウム箔の表面粗さＲａの１．４倍：表面写真を図４に示す）。よって、この方法では、表面が平坦なアルミニウム箔しか得ることができず、粗面を有するアルミニウム箔は得られないことがわかった。
Comparative Example 1:
An aluminum film having a thickness of about 15 μm was formed on the entire surface of the rolled aluminum foil in the same manner as in Example 1 except that the water content of the plating solution was adjusted to 4 ppm. The surface roughness Ra of the aluminum coating thus formed on the surface of the rolled aluminum foil was 1.1 μm (1.4 times the surface roughness Ra of the aluminum foil used as the substrate: a surface photograph is shown in FIG. ). Therefore, it was found that by this method, only an aluminum foil having a flat surface can be obtained, and an aluminum foil having a rough surface cannot be obtained.
比較例２：
めっき液の含水量を８ｐｐｍに調整すること以外は実施例３と同様にして、圧延アルミニウム箔の表面全体に膜厚が約２μｍのアルミニウム被膜を形成した。こうして圧延アルミニウム箔の表面に形成されたアルミニウム被膜の表面粗さＲａは１．４μｍであった（基材として用いたアルミニウム箔の表面粗さＲａの１．８倍）。よって、この方法では、表面が平坦なアルミニウム箔しか得ることができず、粗面を有するアルミニウム箔は得られないことがわかった。
Comparative Example 2:
An aluminum film having a thickness of about 2 μm was formed on the entire surface of the rolled aluminum foil in the same manner as in Example 3 except that the water content of the plating solution was adjusted to 8 ppm. The surface roughness Ra of the aluminum film thus formed on the surface of the rolled aluminum foil was 1.4 μm (1.8 times the surface roughness Ra of the aluminum foil used as the substrate). Therefore, it was found that by this method, only an aluminum foil having a flat surface can be obtained, and an aluminum foil having a rough surface cannot be obtained.
比較例３：
めっき液の含水量を２５００ｐｐｍに調整すること以外は実施例２と同様にして、圧延アルミニウム箔の表面全体にアルミニウム被膜を形成しようとしたが、圧延アルミニウム箔の表面には水洗によって容易に溶出してしまう黒色の被膜が形成されてしまい、アルミニウム被膜を形成することができなかった。
Comparative Example 3:
An aluminum film was formed on the entire surface of the rolled aluminum foil in the same manner as in Example 2 except that the water content of the plating solution was adjusted to 2500 ppm. However, the surface of the rolled aluminum foil was easily eluted by washing with water. As a result, a black film was formed, and an aluminum film could not be formed.
応用例１：本発明の粗面を有するアルミニウム箔を蓄電デバイス用正極集電体として利用した蓄電デバイスの作製
実施例１で得た粗面を有するアルミニウム箔を正極集電体として利用し、その表面に正極活物質を塗布したものを正極として、自体公知の構成を有する蓄電デバイスを作製した。
Application Example 1: Production of an electricity storage device using the aluminum foil having a rough surface of the present invention as a positive electrode current collector for an electricity storage device Using the aluminum foil having a rough surface obtained in Example 1 as a positive electrode current collector, An electricity storage device having a configuration known per se was produced using a positive electrode active material applied to the surface as a positive electrode.
本発明は、蓄電デバイスの正極集電体などとして用いることができる、粗面を有するアルミニウム箔を提供することができる点において産業上の利用可能性を有する。
The present invention has industrial applicability in that it can provide an aluminum foil having a rough surface that can be used as a positive electrode current collector of an electricity storage device.
Claims (10)
An electrical storage device comprising the electrical storage device electrode according to claim 9.
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| KR101958507B1 (en) | 2011-10-27 | 2019-03-14 | 히타치 긴조쿠 가부시키가이샤 | Method for manufacturing porous aluminum foil, porous aluminum foil, positive electrode collector for electricity storage device, electrode for electricity storage device, and electricity storage device |
| DE102012103834A1 (en) * | 2012-05-02 | 2013-11-07 | Hydro Aluminium Rolled Products Gmbh | Textured current collector foil |
| JP2014075205A (en) * | 2012-10-03 | 2014-04-24 | Hitachi Metals Ltd | Power storage device |
| KR101701785B1 (en) | 2013-07-10 | 2017-02-02 | 히타치 긴조쿠 가부시키가이샤 | Collector for lithium ion secondary batteries and positive electrode for lithium ion secondary batteries |
| KR101550044B1 (en) | 2013-07-16 | 2015-09-04 | 삼화전기주식회사 | Sheet, sheet manufacturing method and metal capacitor using the same |
| JP6427893B2 (en) * | 2014-02-20 | 2018-11-28 | 日立金属株式会社 | Electrolytic aluminum foil, current collector for power storage device, electrode for power storage device, power storage device |
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