JP5498750B2 - Aluminum through foil and method for producing the same - Google Patents
Aluminum through foil and method for producing the same Download PDFInfo
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- JP5498750B2 JP5498750B2 JP2009228365A JP2009228365A JP5498750B2 JP 5498750 B2 JP5498750 B2 JP 5498750B2 JP 2009228365 A JP2009228365 A JP 2009228365A JP 2009228365 A JP2009228365 A JP 2009228365A JP 5498750 B2 JP5498750 B2 JP 5498750B2
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- 239000011888 foil Substances 0.000 title claims description 249
- 229910052782 aluminium Inorganic materials 0.000 title claims description 76
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 230000035699 permeability Effects 0.000 claims description 31
- 238000012545 processing Methods 0.000 claims description 24
- 230000035515 penetration Effects 0.000 claims description 22
- 230000000149 penetrating effect Effects 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 10
- 238000005452 bending Methods 0.000 claims description 9
- 238000010998 test method Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 description 63
- 238000000034 method Methods 0.000 description 43
- 238000005096 rolling process Methods 0.000 description 30
- 230000008569 process Effects 0.000 description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 23
- 229910001416 lithium ion Inorganic materials 0.000 description 23
- 238000000137 annealing Methods 0.000 description 22
- 230000037303 wrinkles Effects 0.000 description 17
- 239000003990 capacitor Substances 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000011149 active material Substances 0.000 description 9
- 238000005097 cold rolling Methods 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000012937 correction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000003486 chemical etching Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 229910018084 Al-Fe Inorganic materials 0.000 description 2
- 229910018192 Al—Fe Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000866 electrolytic etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000001741 Ammonium adipate Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Description
本発明は、新規なアルミニウム貫通箔に関する。より具体的には、リチウムイオン電池、リチウムイオンキャパシタ、電気二重層キャパシタ等の集電体に好適に用いられるアルミニウム貫通箔に関する。 The present invention relates to a novel aluminum penetration foil. More specifically, the present invention relates to an aluminum penetrating foil suitably used for a current collector such as a lithium ion battery, a lithium ion capacitor, or an electric double layer capacitor.
リチウムイオン電池、リチウムイオンキャパシタ、電気二重層キャパシタ等のエネルギー密度を向上させるためにはより高い電圧が必要である。エネルギー密度を高めるためには、プレドープ技術を利用し、負極電位を下げることが好ましい。プレドープを効率良く行うためには、集電体に貫通孔を設けることが必要である。集電体の貫通孔を通じてリチウムイオンを可逆的に移動可能とすることにより負極活物質にリチウムイオンを担持することができる。 Higher voltages are required to improve the energy density of lithium ion batteries, lithium ion capacitors, electric double layer capacitors, and the like. In order to increase the energy density, it is preferable to use a pre-doping technique and lower the negative electrode potential. In order to efficiently perform pre-doping, it is necessary to provide a through hole in the current collector. Lithium ions can be supported on the negative electrode active material by allowing lithium ions to move reversibly through the through holes of the current collector.
貫通孔を有する集電体の作製方法として、例えばパンチング加工、メッシュ加工、エキスパンド加工、網加工等が知られているが、これらの方法で形成される貫通孔の大きさは一般的に０．３ｍｍ以上である。ところが、貫通孔を設けるとそれだけ集電体の強度が低下することになり、前記のような比較的大きな孔径では強度低下の問題がより大きくなる。 As a method for producing a current collector having a through hole, for example, punching, meshing, expanding, and netting are known. The size of the through hole formed by these methods is generally 0. 0. 3 mm or more. However, if a through hole is provided, the strength of the current collector is reduced accordingly, and the problem of strength reduction becomes greater with a relatively large hole diameter as described above.
これに対し、比較的微細な貫通孔を有する集電体を用いる電極等が提案されている。例えば、リチウムイオン及び／又はアニオンを可逆的に担持可能な物質からなる正極とリチウムイオンを可逆的に担持可能な物質からなる負極を備えており、かつ、電解液としてリチウム塩の非プロトン性有機溶媒電解質溶液を備えたリチウムイオンキャパシタであって、（１）負極及び／又は正極とリチウムイオン供給源との電気化学的接触によってリチウムイオンが負極及び／又は正極にドーピングされ、（２）正極と負極を短絡させた後の正極の電位が２．０Ｖ以下であり、（３）前記正極及び／又は負極が、表裏面を貫通する多数の孔を有し、かつこれらの貫通孔の内接円の平均直径が１００μｍ以下である金属箔からなる集電体を有することを特徴とするリチウムイオンキャパシタが知られている（特許文献１）。 On the other hand, an electrode using a current collector having relatively fine through holes has been proposed. For example, a positive electrode made of a material capable of reversibly supporting lithium ions and / or anions and a negative electrode made of a material capable of reversibly supporting lithium ions are provided, and an aprotic organic lithium salt is used as an electrolyte. A lithium ion capacitor comprising a solvent electrolyte solution, wherein (1) lithium ions are doped into the negative electrode and / or positive electrode by electrochemical contact between the negative electrode and / or positive electrode and a lithium ion supply source; The potential of the positive electrode after short-circuiting the negative electrode is 2.0 V or less, (3) the positive electrode and / or the negative electrode has a large number of holes penetrating the front and back surfaces, and an inscribed circle of these through holes There is known a lithium ion capacitor having a current collector made of a metal foil having an average diameter of 100 μm or less (Patent Document 1).
また、厚さが２０〜４５μｍ及び見掛密度が２．００〜２．５４ｇ／ｃｍ３で、透気度２０〜１２０ｓの表裏面を貫通する多数の貫通孔を有するアルミニウムエッチング箔よりなる集電体と、この集電体上に、活物質として、リチウムイオン及びアニオンを可逆的に担持可能な物質を含有する塗料が塗布されることによって形成された電極層とを有することを特徴とする塗布電極であって、前記集電体の貫通孔の８０％以上が、孔径１〜３０μｍであることを特徴とする塗布電極が知られている（特許文献２）。その他にも、結晶方位が揃ったアルミニウム箔として、電解コンデンサ用アルミニウム箔が知られている（例えば、特許文献３、特許文献４）。 Further, the current collector is made of an aluminum etching foil having a thickness of 20 to 45 μm, an apparent density of 2.00 to 2.54 g / cm 3 , and a large number of through holes penetrating the front and back surfaces having an air permeability of 20 to 120 s. And an electrode layer formed by applying a paint containing a material capable of reversibly supporting lithium ions and anions as an active material on the current collector A coated electrode is known in which 80% or more of the through-holes of the current collector have a hole diameter of 1 to 30 μm (Patent Document 2). In addition, aluminum foil for electrolytic capacitors is known as an aluminum foil having a uniform crystal orientation (for example, Patent Document 3 and Patent Document 4).
しかしながら、アルミニウム箔に貫通孔を多数形成した場合、必然的にそれだけ箔強度は低下することになる。このことは前記の従来技術においても例外ではなく、箔強度が貫通孔の形成に伴って低下する結果、後工程で活物質をアルミニウム箔に塗工する際において箔切れ又はシワの発生が生じるおそれがある。たとえ問題なく塗工できて製品化したとしても、製品に加わる衝撃等によりアルミニウム箔が破断しやすくなる。これらの問題は、アルミニウム箔の厚みが小さくなるほどより深刻になる。 However, when many through holes are formed in the aluminum foil, the foil strength inevitably decreases accordingly. This is not an exception even in the above-described conventional technology, and as a result of the foil strength decreasing with the formation of the through-hole, there is a risk of occurrence of foil breakage or wrinkles when the active material is applied to the aluminum foil in the subsequent step. There is. Even if it can be applied without problems and commercialized, the aluminum foil tends to break due to impact applied to the product. These problems become more serious as the thickness of the aluminum foil decreases.
一方、電池及びキャパシタは、高エネルギー密度・高出力密度とともに、軽量・小型化も強く求められている。このような要請に伴って、集電体の厚みもより小さくできるよう求められている。 On the other hand, batteries and capacitors are strongly required to be light and small in size as well as high energy density and high power density. With such a demand, there is a demand for reducing the thickness of the current collector.
このように、集電体等としての性能を高めるためには貫通孔を多数形成することが望まれるものの、それに伴い箔強度の低下、ひいては後工程でのトラブル等を招くことになる。ここで、エッチングに使用する箔の強度を高める方法としては、合金元素添加（例えばＦｅ、Ｃｕ、Ｍｎ、Ｍｇ、Ｔｉなど）による方法のほか、熱処理の条件による方法等があるが、いずれもエッチング性を阻害するので最善の方法とは言えない。エッチング性の阻害とは、エッチングピットの伸びを阻害したり、過剰な溶解が起こり正常な溶解を維持できなくなる状態を言う。従来の３００３材等で代表される高強度アルミニウム箔では、表面から裏面までを貫通するピットを多数制御するのは困難である。エッチング前に加工等を行い、強度を付与することも考えられるが、この方法ではエッチングピットの発生又は成長を阻害し、強度と透気度のバランスが悪くなる。 As described above, in order to improve the performance as a current collector or the like, it is desired to form a large number of through-holes, but this causes a decrease in foil strength and, consequently, troubles in subsequent processes. Here, as a method for increasing the strength of the foil used for etching, there are methods based on heat treatment conditions in addition to methods using alloying elements (for example, Fe, Cu, Mn, Mg, Ti, etc.). It's not the best way to prevent sex. Etching inhibition refers to a state where etching pit elongation is inhibited or excessive dissolution occurs and normal dissolution cannot be maintained. With a high-strength aluminum foil represented by a conventional 3003 material, it is difficult to control a large number of pits penetrating from the front surface to the back surface. Although it is conceivable to perform processing or the like before etching to impart strength, this method inhibits the generation or growth of etching pits, and the balance between strength and air permeability deteriorates.
以上のように、貫通孔を多数するにもかかわらず、所望の箔強度を発揮できるアルミニウム箔は未だ開発されるに至っていないのが現状である。 As described above, in spite of the large number of through holes, an aluminum foil that can exhibit a desired foil strength has not yet been developed.
従って、本発明の主な目的は、貫通孔を多数するとともに所望の箔強度を有するアルミニウム箔を提供することにある。 Accordingly, a main object of the present invention is to provide an aluminum foil having a large number of through holes and a desired foil strength.
本発明者は、従来技術の問題点に鑑みて鋭意研究を重ねた結果、貫通孔を有するアルミニウム箔を所定の加工処理を施すことにより、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by subjecting an aluminum foil having a through hole to a predetermined processing, thereby completing the present invention. It came.
すなわち、本発明は、下記のアルミニウム貫通箔及びその製造方法に係る。
１． 箔表面から裏面に至る貫通孔を複数有するアルミニウム貫通箔であって、
（１）箔厚みが５０μｍ以下であり、
（２）破断強度が［０．２×箔厚み（μｍ）］Ｎ／１０ｍｍ以上であり、
（３）［耐力値／破断強度］が５０％以上であり、
（４）Ｆｅ：５〜８０重量ｐｐｍ、Ｓｉ：５〜１００重量ｐｐｍ、Ｃｕ：１０〜１００重量ｐｐｍならびに残部：Ａｌ及び不可避不純物からなる組成を有する、
ことを特徴とする高強度アルミニウム貫通箔。
２． ＪＩＳ Ｐ ８１１７に準じたガーレ式デンソメータによる透気度試験方法によって測定された透気度が５ｓｅｃ／１００ｍｌ以上である、前記項１に記載の高強度アルミニウム貫通箔。
３． 貫通孔の内径が０．２〜５μｍである、前記項１又は２に記載の高強度アルミニウム貫通箔。
４． 表面積拡大比が、
［０．１０×箔厚み（μｍ）］以上の値である、前記項１〜３のいずれかに記載の高強度アルミニウム貫通箔。
５． アルミニウム貫通箔における垂直貫通孔占有率ｃ（％）と前記箔厚みｔ（μｍ）の比率［ｃ／ｔ］が１．４以上である、前記項１〜４のいずれかに記載の高強度アルミニウム貫通箔。
６． 箔表面から裏面に至る貫通孔を複数有するアルミニウム貫通箔に対し、引張加工と曲げ加工とを同時に行う工程を含むことを特徴とする高強度アルミニウム貫通箔の製造方法であって、
高強度アルミニウム貫通箔が、
（１）箔厚みが５０μｍ以下であり、
（２）破断強度が［０．２×箔厚み（μｍ）］Ｎ／１０ｍｍ以上であり、
（３）［耐力値／破断強度］が５０％以上であり、
（４）Ｆｅ：５〜８０重量ｐｐｍ、Ｓｉ：５〜１００重量ｐｐｍ、Ｃｕ：１０〜１００重量ｐｐｍならびに残部：Ａｌ及び不可避不純物からなる組成を有する、
ことを特徴とする製造方法。
That is, this invention relates to the following aluminum penetration foil and its manufacturing method.
1. An aluminum through foil having a plurality of through holes from the foil surface to the back surface,
(1) The foil thickness is 50 μm or less,
(2) The breaking strength is [0.2 × foil thickness (μm)] N / 10 mm or more,
(3) [proof value / breaking strength] is 50% or more ,
(4) Fe: 5 to 80 ppm by weight, Si: 5 to 100 ppm by weight, Cu: 10 to 100 ppm by weight and the balance: Al and inevitable impurities,
A high-strength aluminum penetration foil characterized by that.
2. Item 2. The high-strength aluminum penetrating foil according to Item 1, wherein the air permeability measured by a gas permeability test method using a Gurley-type densometer according to JIS P 8117 is 5 sec / 100 ml or more.
3. Item 3. The high-strength aluminum penetrating foil according to Item 1 or 2, wherein the through hole has an inner diameter of 0.2 to 5 µm.
4). The surface area expansion ratio is
Item 4. The high-strength aluminum penetrating foil according to any one of Items 1 to 3, which has a value of [0.10 × foil thickness (μm)] or more.
5. Item 5. The high-strength aluminum according to any one of Items 1 to 4 , wherein a ratio [c / t] of the vertical through-hole occupation ratio c (%) and the foil thickness t (μm) in the aluminum through foil is 1.4 or more. Penetration foil.
6). To aluminum penetration foil having a plurality of through holes extending from the foil surface on the back, I manufacturing method der high strength aluminum through foil which comprises a step of performing a tensile processing and bending at the same time,
High strength aluminum penetration foil
(1) The foil thickness is 50 μm or less,
(2) The breaking strength is [0.2 × foil thickness (μm)] N / 10 mm or more,
(3) [proof value / breaking strength] is 50% or more,
(4) Fe: 5 to 80 ppm by weight, Si: 5 to 100 ppm by weight, Cu: 10 to 100 ppm by weight and the balance: Al and inevitable impurities,
The manufacturing method characterized by the above-mentioned.
本発明によれば、箔厚みが５０μｍ以下（特に２５μｍ以下）と薄くても、集電体等として優れた特性を得るのに十分な貫通孔を有するとともに、後工程を円滑に行うことができる強度を兼ね備えたアルミニウム貫通箔を提供することができる。すなわち、本発明の高強度アルミニウム貫通箔は、破断強度が［０．２×箔厚み（μｍ）］Ｎ／１０ｍｍ以上であり、かつ、［耐力値／破断強度］（破断強度に対する耐力値の割合）が５０％以上という優れた特性を発揮することができる。 According to the present invention, even if the foil thickness is as thin as 50 μm or less (particularly 25 μm or less), it has sufficient through holes to obtain excellent characteristics as a current collector and the like, and the subsequent process can be performed smoothly. The aluminum penetration foil which has intensity | strength can be provided. That is, the high-strength aluminum penetrating foil of the present invention has a breaking strength of [0.2 × foil thickness (μm)] N / 10 mm or more, and [proof strength value / breaking strength] (ratio of strength value to breaking strength). ) Can exhibit an excellent characteristic of 50% or more.
このようなアルミニウム貫通箔は、リチウムイオン電池、リチウムイオンキャパシタ、電気二重層キャパシタ等の集電体として好適に用いることができる。とりわけ、リチウムイオンキャパシタ又はリチウムイオン二次電池が、１）リチウムイオン及び／又はアニオンを可逆的に担持可能な物質からなる正極、２）リチウムイオンを可逆的に担持可能な物質からなる負極及び３）リチウムイオンを含む電解質溶液を含み、かつ、リチウムイオンが正極及び／又は負極にドーピングされるものの集電体として本発明のアルミニウム貫通箔は有用である。 Such an aluminum penetration foil can be suitably used as a current collector for a lithium ion battery, a lithium ion capacitor, an electric double layer capacitor or the like. In particular, a lithium ion capacitor or a lithium ion secondary battery includes 1) a positive electrode made of a material capable of reversibly carrying lithium ions and / or anions, and 2) a negative electrode made of a material capable of reversibly carrying lithium ions and 3 The aluminum through-foil of the present invention is useful as a current collector that contains an electrolyte solution containing lithium ions and is doped with lithium ions on the positive electrode and / or the negative electrode.
１．高強度アルミニウム貫通箔
本発明の高強度アルミニウム貫通箔（本発明Ａｌ箔）は、箔表面から裏面に至る貫通孔を複数有するアルミニウム貫通箔であって、
（１）箔厚みが５０μｍ以下であり、
（２）破断強度が［０．２×箔厚み（μｍ）］Ｎ／１０ｍｍ以上であり、
（３）［耐力値／破断強度］が５０％以上である、
ことを特徴とする。
1. High-strength aluminum penetrating foil The high-strength aluminum penetrating foil of the present invention (present Al foil) is an aluminum penetrating foil having a plurality of through-holes from the foil surface to the back surface,
(1) The foil thickness is 50 μm or less,
(2) The breaking strength is [0.2 × foil thickness (μm)] N / 10 mm or more,
(3) [proof value / breaking strength] is 50% or more,
It is characterized by that.
本発明Ａｌ箔は、箔表面から裏面に至る貫通孔を複数有するものである。図１には、本発明Ａｌ箔の断面の模式図を示す。例えば、図１に示すように、本発明Ａｌ箔１において、その箔表面１１から裏面１２に至る貫通孔２を複数有する。このような貫通孔は、エッチング処理を施すことによって形成することができる。 The Al foil of the present invention has a plurality of through holes from the foil surface to the back surface. In FIG. 1, the schematic diagram of the cross section of this invention Al foil is shown. For example, as shown in FIG. 1, the Al foil 1 of the present invention has a plurality of through holes 2 extending from the foil surface 11 to the back surface 12. Such a through hole can be formed by performing an etching process.
貫通孔
貫通孔の内径は、Ａｌ箔の用途、使用目的等に応じて適宜設定することができるが、通常は０．２〜５μｍ、特に０．５〜３μｍとすることが好ましい。貫通孔の内径は、エッチング処理時において特にエッチング時間を調整することにより適宜制御することができる。
The inner diameter of the through-hole through holes, Al foil applications and can be set appropriately according to the intended use or the like, usually 0.2 to 5 .mu.m, it is preferable in particular with 0.5 to 3 [mu] m. The inner diameter of the through hole can be appropriately controlled by adjusting the etching time particularly during the etching process.
貫通孔の存在割合としては特に限定的ではないが、一般的にはＪＩＳ Ｐ ８１１７に準じたガーレ式デンソメータによる透気度試験方法によって測定された透気度が５ｓｅｃ／１００ｍｌ以上、特に３０ｓｅｃ／１００ｍｌ以上であることが好ましい。かかる透気度を有することにより、本発明Ａｌ箔に活物質を塗布しても活物質が裏抜けせず、不必要な部分にも活物質が塗布されることがないため、その対策としての前処理が不要になるという効果が得られる。なお、前記透気度の上限値は特に制限されないが、通常は５００ｓｅｃ／１００ｍｌ程度とすれば良い。 Although there is no particular limitation on the existence ratio of the through holes, generally the air permeability measured by the air permeability test method using a Gurley type densometer according to JIS P 8117 is 5 sec / 100 ml or more, particularly 30 sec / 100 ml. The above is preferable. By having such air permeability, even if an active material is applied to the Al foil of the present invention, the active material does not get through, and the active material is not applied to unnecessary portions. The effect that pre-processing becomes unnecessary is acquired. The upper limit value of the air permeability is not particularly limited, but is usually about 500 sec / 100 ml.
本発明Ａｌ箔では、アルミニウム貫通箔における垂直貫通孔占有率ｃ（％）と前記箔厚みｔ（μｍ）の比率［ｃ／ｔ］が１．４以上であり、好ましくは１．５以上であり、より好ましくは１．６以上である。このことは、本発明Ａｌ箔が、従来のアルミニウム貫通箔と比べて、同じ厚みでもより高い垂直貫通孔占有率を示すものである。すなわち、本発明Ａｌ箔は、厚みが薄いにもかかわらず、より高い垂直貫通孔占有率を有するものである。一般に、高純度アルミニウム箔は、厚くが薄くなるほど立方体方位占有率が低くなり、それに伴って垂直貫通孔占有率も低下する。一般的には立方体方位占有率は、箔厚み（μｍ）％の数値程度の値に相当すると言われている。例えば、箔厚み５５μｍのアルミニウム箔であれば立方体方位占有率はおよそ５５％前後となる。これに対し、本発明では、Ｆｅ、Ｓｉ、Ｃｕ等の含有量を制御すること等によって、薄い箔であっても従来技術よりも高い立方体方位占有率を実現させることができる結果、垂直貫通孔占有率をより高くすることが可能となる。 In the Al foil of the present invention, the ratio [c / t] of the vertical through-hole occupation ratio c (%) and the foil thickness t (μm) in the aluminum through foil is 1.4 or more, preferably 1.5 or more. More preferably, it is 1.6 or more. This indicates that the Al foil of the present invention exhibits a higher vertical through-hole occupation ratio even at the same thickness as compared with the conventional aluminum through foil. That is, the Al foil of the present invention has a higher vertical through-hole occupancy rate despite its small thickness. In general, as the thickness of the high-purity aluminum foil increases, the cube orientation occupancy decreases, and the vertical through-hole occupancy decreases accordingly. In general, it is said that the cube orientation occupancy corresponds to a value about the value of foil thickness (μm)%. For example, in the case of an aluminum foil having a foil thickness of 55 μm, the cube orientation occupation ratio is approximately 55%. On the other hand, in the present invention, by controlling the content of Fe, Si, Cu, etc., it is possible to realize a higher cubic orientation occupancy than the prior art even with a thin foil. It becomes possible to increase the occupation ratio.
前記の垂直貫通孔占有率に関し、本発明Ａｌ箔では垂直貫通孔占有率そのものの値については箔厚み等によって変動するので特に限定されないが、一般的には３０〜９８％、特に４０〜９８％の範囲内にあれば良い。 Regarding the vertical through-hole occupancy, the value of the vertical through-hole occupancy itself in the Al foil of the present invention varies depending on the foil thickness and the like, but is not particularly limited, but is generally 30 to 98%, particularly 40 to 98%. If it is in the range.
なお、一般に、水平面から７０〜１１０度の角度をなす貫通孔の割合が、エッチング前のアルミニウム箔の立方体方位占有率とほぼ同じ値となることから、本発明では貫通孔が水平面から７０〜１１０度（すなわち、９０度±２０度）の範囲の角度をなすものを垂直貫通孔とし、貫通孔の総数に対する垂直貫通孔が占める割合を垂直貫通孔占有率としている。よって、本発明のおける垂直貫通孔占有率は、エッチング前のアルミニウム箔の立方体方位占有率とほぼ同じ値となる。 In general, since the ratio of the through holes forming an angle of 70 to 110 degrees from the horizontal plane is substantially the same as the cube orientation occupation ratio of the aluminum foil before etching, in the present invention, the through holes are 70 to 110 from the horizontal plane. A vertical through hole is defined as an angle having an angle in the range of degrees (that is, 90 ° ± 20 °), and the ratio of the vertical through hole to the total number of through holes is defined as the vertical through hole occupation ratio. Therefore, the vertical through-hole occupation ratio in the present invention is almost the same value as the cube orientation occupation ratio of the aluminum foil before etching.
本発明Ａｌ箔においては、表面積拡大比が［０．１５×箔厚みｔ（μｍ）］以上の値、特に［０．１７×箔厚みｔ（μｍ）］以上の値であることが好ましい。表面拡大比を上記範囲に設定することによって、集電体としての本発明Ａｌ箔と活物質との密着性が向上する。 In the Al foil of the present invention, the surface area expansion ratio is preferably a value of [0.15 × foil thickness t (μm)] or more, particularly preferably a value of [0.17 × foil thickness t (μm)] or more. By setting the surface expansion ratio within the above range, the adhesion between the Al foil of the present invention as a current collector and the active material is improved.
また、本発明Ａｌ箔では、貫通孔率ｓ（％）＝〔測定重量（ｇ）／〔箔厚み（ｃｍ）×試料面積（ｃｍ２）〕〕／アルミニウムの比重（２．７０ｇ／ｃｍ３）が、５≦ｓ≦２０の範囲にあることが好ましい。上記範囲内に設定することによって、貫通孔を通じてリチウムイオンを可逆的に移動可能でありながら、強度が低くなりすぎるおそれがない。 Further, in the Al foil of the present invention, the through porosity s (%) = [measured weight (g) / [foil thickness (cm) × sample area (cm 2 )]] / aluminum specific gravity (2.70 g / cm 3 ) Is preferably in the range of 5 ≦ s ≦ 20. By setting within the above range, the lithium ion can be reversibly moved through the through hole, but there is no possibility that the strength becomes too low.
本発明Ａｌ箔の厚みは、通常は５０μｍ以下、好ましくは４０μｍ以下、さらに好ましくは２５μｍ以下とする。上記の厚みに設定することにより、リチウムイオンキャパシタの集電体として好適に用いることができる。なお、厚みの下限値は限定的ではないが、通常は１μｍ程度とすれば良い。 The thickness of the Al foil of the present invention is usually 50 μm or less, preferably 40 μm or less, more preferably 25 μm or less. By setting to the above thickness, it can be suitably used as a current collector of a lithium ion capacitor. The lower limit value of the thickness is not limited, but is usually about 1 μm.
破断強度及び耐力値
本発明Ａｌ箔は、破断強度が［０．２×箔厚み（μｍ）］Ｎ／１０ｍｍ以上であり、好ましくは［０．２５×箔厚み（μｍ）］Ｎ／１０ｍｍ以上である。例えば、箔厚みが５０μｍの本発明Ａｌ箔では、破断強度は１０Ｎ／１０ｍｍ以上である。破断強度は、一般的には箔厚みの減少とともに低下するが、本発明ではその低下度合いが小さく、同じ箔厚みでは従来品に比して高い破断強度を示す。本発明Ａｌ箔では、厚み３０〜５０μｍでは破断強度は８〜１５Ｎ／１０ｍｍ程度と比較的高強度であるが、それ以上の高い破断強度であっても良い。なお、破断強度の上限値は限定的ではないが、箔厚み５０μｍ以下の範囲であれば通常は５０Ｎ／１０ｍｍ程度、箔厚み２５μｍ以下の範囲であれば通常は２５Ｎ／１０ｍｍ程度である。
Breaking strength and proof stress value The Al foil of the present invention has a breaking strength of [0.2 × foil thickness (μm)] N / 10 mm or more, preferably [0.25 × foil thickness (μm)] N / 10 mm or more. is there. For example, in the Al foil of the present invention having a foil thickness of 50 μm, the breaking strength is 10 N / 10 mm or more. The breaking strength generally decreases as the foil thickness decreases, but in the present invention, the degree of decrease is small, and the same foil thickness shows a higher breaking strength than the conventional product. The Al foil of the present invention has a relatively high breaking strength of about 8 to 15 N / 10 mm at a thickness of 30 to 50 μm, but may have a higher breaking strength. The upper limit of the breaking strength is not limited, but is usually about 50 N / 10 mm when the foil thickness is 50 μm or less, and is usually about 25 N / 10 mm when the foil thickness is 25 μm or less.
また、本発明Ａｌ箔における［耐力値／破断強度］（破断強度に対する耐力値の割合）の値は５０％以上、好ましくは７０％以上である。前記値が５０％未満の場合は、ハンドリング性等が低下する結果、後工程において箔の破断、シワ等の発生を高頻度でもたらすおそれがある。本発明Ａｌ箔の耐力値（一般に材料の引っ張り試験を行った時に０．２％伸びた時の抗張力を言う。）は、箔厚みが３０〜５０μｍの範囲内においては通常２〜５Ｎ／１０ｍｍ程度であるが、この範囲を上回る場合も本発明に包含される。本発明では、このような高い耐力値、ひいては前記割合を高くすることにより、ハンドリング性を良くし、箔切れあるいはシワの発生を抑制することができる。 Moreover, the value of [proof value / breaking strength] (ratio of yield value to breaking strength) in the Al foil of the present invention is 50% or more, preferably 70% or more. When the value is less than 50%, the handleability and the like are deteriorated, and as a result, the foil may be frequently broken and wrinkled in the subsequent process. The proof stress value of the Al foil of the present invention (generally speaking, the tensile strength when the material is stretched by 0.2% when a tensile test is performed) is usually about 2 to 5 N / 10 mm when the foil thickness is in the range of 30 to 50 μm. However, cases exceeding this range are also encompassed by the present invention. In the present invention, by increasing such a high proof stress value and thus the ratio, it is possible to improve the handling property and suppress the occurrence of foil breakage or wrinkles.
組成
本発明Ａｌ箔の組成は、上記の特性を有する限りは制限されず、公知のＡｌ箔における組成を採用することもできるが、特にＦｅ：５〜８０重量ｐｐｍ、Ｓｉ：５〜１００重量ｐｐｍ、Ｃｕ：１０〜１００重量ｐｐｍならびに残部：Ａｌ及び不可避不純物からなる組成を好適に採用することができる。
Composition The composition of the Al foil of the present invention is not limited as long as it has the above-mentioned characteristics, and a composition in a known Al foil can be adopted, but in particular, Fe: 5 to 80 ppm by weight, Si: 5 to 100 ppm by weight Cu: 10 to 100 ppm by weight and the balance: Al and inevitable impurities can be suitably employed.
Ｆｅの含有量は、通常５〜８０ｐｐｍ程度とし、好ましくは１０〜５０ｐｐｍとする。Ｆｅは、Ａｌ−Ｆｅ系の化合物として晶出し、圧延性や伸びを改善することができる元素である。また、適度な量のＡｌ−Ｆｅ系の化合物は、結晶核発生サイド及びピン止めにより結晶粒を微細化し、薄箔の圧延性を向上させる。 The content of Fe is usually about 5 to 80 ppm, preferably 10 to 50 ppm. Fe is an element that can be crystallized as an Al—Fe-based compound and can improve rolling properties and elongation. In addition, an appropriate amount of the Al—Fe-based compound refines the crystal grains by the crystal nucleus generation side and pinning, and improves the rollability of the thin foil.
Ｆｅの含有量が５ｐｐｍ未満の場合は、上記の効果が得られず、結晶粒の粗大化による箔の強度低下が起こり、孔開箔の強度低下や部位による強度のバラツキを生じやすい。一方、Ｆｅの含有量が８０ｐｐｍを超える場合は、表面に過剰な溶解が起こり、孔開箔の強度低下や部位による強度のバラツキを招く。また、立方体方位の占有率が低くなり、十分な貫通エッチングピット密度が得られなくなる。 When the Fe content is less than 5 ppm, the above effect cannot be obtained, and the strength of the foil is reduced due to the coarsening of crystal grains, and the strength of the perforated foil is easily reduced and the strength varies depending on the part. On the other hand, when the Fe content exceeds 80 ppm, excessive dissolution occurs on the surface, resulting in a decrease in strength of the perforated foil and variation in strength due to the site. Further, the occupation ratio of the cube orientation is lowered, and a sufficient through etching pit density cannot be obtained.
Ｓｉの含有量は、通常５〜１００ｐｐｍ程度とし、好ましくは１０〜６０ｐｐｍとする。Ｓｉは、主に、強度を向上させることができる元素である。また、例えば、特に厚みが５０μｍ以下の薄箔への圧延時にはアルミニウム貫通箔の表面のみならず、内部にも圧延加工に伴う瞬間的な温度上昇が発生するが、シリコンの存在により転位の消失を抑制して強度の低下を防ぐことができる。 The Si content is usually about 5 to 100 ppm, preferably 10 to 60 ppm. Si is an element that can mainly improve the strength. In addition, for example, when rolling to a thin foil having a thickness of 50 μm or less, an instantaneous temperature rise is caused not only on the surface of the aluminum penetrating foil but also on the inside, but dislocation disappears due to the presence of silicon. It can suppress and the fall of intensity | strength can be prevented.
Ｓｉの含有量が５ｐｐｍ未満の場合は、上記の効果が得られず、強度低下が起こり、孔開箔の強度低下や部位による強度のバラツキを生じやすい。また、Ｓｉの含有量が１００ｐｐｍを超える場合は、立方体方位の占有率が低くなり、十分な貫通エッチングピット密度が得られない。 When the Si content is less than 5 ppm, the above effects cannot be obtained, and the strength is lowered, and the strength of the perforated foil is easily reduced and the strength varies depending on the portion. In addition, when the Si content exceeds 100 ppm, the occupation ratio of the cube orientation becomes low, and a sufficient through etching pit density cannot be obtained.
Ｃｕの含有量は、通常１０〜１００ｐｐｍ程度とし、好ましくは１５〜６０ｐｐｍとする。Ｃｕの含有量が上記範囲に設定されている場合は、特に箔厚み２５μｍ以下に圧延する際の圧延性をより向上させることができる。また、Ｃｕは、塩酸エッチング時の溶解性を向上させ、貫通エッチングピットの形成に寄与する。 The Cu content is usually about 10 to 100 ppm, preferably 15 to 60 ppm. When the Cu content is set within the above range, the rollability when rolling to a foil thickness of 25 μm or less can be further improved. Cu also improves the solubility during hydrochloric acid etching and contributes to the formation of through-etching pits.
Ｃｕの含有量が１０ｐｐｍ未満の場合は上記の効果が十分に得られない上、薄箔の圧延性を著しく低下させる。他方、Ｃｕの含有量が１００ｐｐｍを超える場合は、表面に過剰な溶解が起こり、孔開箔の強度低下や部位による強度のバラツキを招く。また、立方体方位の占有率が低くなり、十分な貫通エッチングピット密度が得られない。 When the Cu content is less than 10 ppm, the above effect cannot be obtained sufficiently and the rollability of the thin foil is remarkably lowered. On the other hand, when the Cu content exceeds 100 ppm, excessive dissolution occurs on the surface, resulting in a decrease in strength of the perforated foil and variation in strength due to the site. Further, the occupation ratio of the cube orientation is lowered, and a sufficient through etching pit density cannot be obtained.
本発明Ａｌ箔では、上記のような成分のほか、必要に応じてＰｂが含まれていても良い。Ｐｂは、主としてエッチング処理に使用する電解液とアルミニウム箔との反応を促進し、初期のエッチングピット数を増加させる働きがあることから、いっそう高い貫通エッチング密度を達成することが可能となる。Ｐｂを含有する場合のＰｂ含有量は、通常０．０１〜２０ｐｐｍ程度とし、好ましくは０．０５〜１０ｐｐｍとすれば良い。 In addition to the above components, the Al foil of the present invention may contain Pb as necessary. Pb mainly promotes the reaction between the electrolytic solution used for the etching process and the aluminum foil and increases the initial number of etching pits, so that a higher penetration etching density can be achieved. When Pb is contained, the Pb content is usually about 0.01 to 20 ppm, preferably 0.05 to 10 ppm.
Ｐｂは、主としてエッチング処理に使用する電解液とアルミニウム箔との反応を促進し、初期のエッチングピット数を増加させる働きがあるので、いっそう高い貫通エッチング密度を達成することが可能となる。Ｐｂを含有する場合のＰｂの含有量は、上記のような効果が達成できるように適宜調整することができるが、通常０．０１〜２０ｐｐｍ程度、好ましくは０．０５〜１０ｐｐｍとすれば良い。 Pb mainly promotes the reaction between the electrolytic solution used for the etching process and the aluminum foil and increases the initial number of etching pits, so that a higher through-etching density can be achieved. The content of Pb in the case of containing Pb can be appropriately adjusted so that the above effects can be achieved, but is usually about 0.01 to 20 ppm, preferably 0.05 to 10 ppm.
特に、本発明Ａｌ箔では、Ｐｂがアルミニウム箔の表面から深さ０．１μｍまでの領域において４０〜２０００ｐｐｍの範囲となるように設定することが望ましい。上記範囲内に設定することによって、貫通エッチング密度をよりいっそう高めることができる。 In particular, in the Al foil of the present invention, it is desirable to set Pb to be in the range of 40 to 2000 ppm in the region from the surface of the aluminum foil to a depth of 0.1 μm. By setting within the above range, the penetration etching density can be further increased.
なお、このようなＰｂ含有量の調整は、例えばアルミニウム箔の製造段階においてアルミニウム溶湯に添加するＰｂ量を調節し、さらに焼鈍温度を４５０℃以上の範囲内で制御することによって実施することができる。 Such adjustment of the Pb content can be carried out, for example, by adjusting the amount of Pb added to the molten aluminum in the production stage of the aluminum foil and further controlling the annealing temperature within a range of 450 ° C. or higher. .
残部は実質的にＡｌと不可避不純物からなる。本発明のアルミニウム合金箔におけるアルミニウム純度は、集電体用として使える範囲内であれば特に制限されない。また、不可避不純物としては、例えばＭｇ、Ｍｎ、Ｚｎ、Ｔｉ、Ｖ、Ｇａ、Ｃｒ、Ｚｒ、Ｂ等が含まれていても良い。 The balance is substantially made of Al and inevitable impurities. The aluminum purity in the aluminum alloy foil of the present invention is not particularly limited as long as it is within a range that can be used for a current collector. Inevitable impurities may include, for example, Mg, Mn, Zn, Ti, V, Ga, Cr, Zr, and B.
２．高強度アルミニウム貫通箔の製造方法
本発明Ａｌ箔は、次のようにして製造することができる。すなわち、箔表面から裏面に至る貫通孔を複数有するアルミニウム貫通箔に対し、引張加工と曲げ加工とを同時に行う（本発明加工）工程を含むことを特徴とする高強度アルミニウム貫通箔の製造方法により、本発明Ａｌ箔を好適に製造することができる。
2. Manufacturing method of high-strength aluminum penetration foil The Al foil of the present invention can be manufactured as follows. That is, by the manufacturing method of the high strength aluminum penetration foil characterized by including the process (this invention process) which performs simultaneously a tension process and a bending process with respect to the aluminum penetration foil which has multiple through-holes from the foil surface to a back surface The Al foil of the present invention can be preferably produced.
前記アルミニウム貫通箔（原箔）は、公知の方法により調製することもできるが、特に以下の方法に従って調製することが望ましい。 Although the said aluminum penetration foil (raw foil) can also be prepared by a well-known method, it is desirable to prepare especially according to the following method.
まず、鋳造から板圧延（約１ｍｍ位）まではほぼ通常の方法で製造することができる。例えば、上記組成を有する原料の溶湯を調製し、溶湯を凝固させることにより鋳塊を製造する。この場合、得られた鋳塊に対して４００〜５５０℃で１〜２０時間程度の均質化処理を施すことが好ましい。特に、本発明では、均質化処理温度を５５０℃以下とすることが望ましい。均質化処理温度を５５０℃以下とすることによって、５０μｍ以下の箔に圧延して焼鈍した後により高い立方体方位占有率を得ることができる。 First, from casting to plate rolling (about 1 mm), it can be manufactured by an ordinary method. For example, an ingot is produced by preparing a molten raw material having the above composition and solidifying the molten metal. In this case, it is preferable to subject the obtained ingot to a homogenization treatment at 400 to 550 ° C. for about 1 to 20 hours. In particular, in the present invention, it is desirable that the homogenization temperature is 550 ° C. or lower. By setting the homogenization treatment temperature to 550 ° C. or lower, a higher cube orientation occupation ratio can be obtained after rolling and annealing to a foil of 50 μm or less.
その後、鋳塊に対して熱間圧延及び冷間圧延を施すことによって３５０μｍ程度の厚箔とする。なお、必要に応じて、板表面の不純物又は酸化皮膜を除去する等の目的で板洗浄、箔洗浄等の公知の処理を行っても良い。 Thereafter, the ingot is hot rolled and cold rolled to obtain a thick foil of about 350 μm. In addition, you may perform well-known processes, such as board washing | cleaning and foil washing | cleaning, for the objective of removing the impurity or oxide film of a board surface as needed.
次いで、前記の厚箔を冷間圧延することによって、薄箔を得る。この場合、圧延後の薄箔の厚みは、最終箔の厚みの１１０〜１３０％の厚みとすることが好ましい。なお、冷間圧延の温度自体は、公知の冷間圧延と同様にすれば良く、例えば１２０℃を超えない温度範囲内で実施することができる。 Next, a thin foil is obtained by cold rolling the thick foil. In this case, the thickness of the thin foil after rolling is preferably 110 to 130% of the thickness of the final foil. In addition, what is necessary is just to make the temperature of cold rolling itself the same as well-known cold rolling, for example, can be implemented within the temperature range which does not exceed 120 degreeC.
薄箔の圧延時にはアルミニウム箔の表面のみならず内部にも、圧延加工に伴う瞬間的な温度上昇が発生する。また、アルミニウム箔と圧延ロールとの間の摩擦等、機械的ストレスが大きくなると、５０μｍ以下の箔に圧延して焼鈍した後に立方体方位の占有率が低くなるおそれがある。従って、薄箔の圧延（少なくとも最後の圧延（すなわち、最終箔を得るための圧延））は、圧延ロールの平均粗度Ｒａを０．２５μｍ以下、特に０．２０μｍ以下、さらには０．１８μｍ以下とすることが好ましい。この場合、得られる薄箔の平均粗度Ｒａは、圧延ロールと接する面がそれぞれ０．２５μｍ以下、特に０．２０μｍ以下、さらに０．１８μｍ以下となる。 When rolling a thin foil, an instantaneous temperature rise accompanying the rolling process occurs not only on the surface of the aluminum foil but also inside. Further, when mechanical stress such as friction between the aluminum foil and the rolling roll increases, the occupation ratio of the cube orientation may decrease after rolling and annealing to a foil of 50 μm or less. Therefore, the thin foil rolling (at least the final rolling (that is, rolling for obtaining the final foil)) has an average roughness Ra of the rolling roll of 0.25 μm or less, particularly 0.20 μm or less, and further 0.18 μm or less. It is preferable that In this case, the average roughness Ra of the thin foil obtained is 0.25 μm or less, particularly 0.20 μm or less, and further 0.18 μm or less on the surface in contact with the rolling roll.
本発明では、厚箔を圧延して薄箔を得る場合は、圧延ロールに接触しない面を確保しながら圧延することが好ましい。圧延ロールに接触しない面を確保することにより、結晶粒の動きを阻害する要因を除くことができ、これにより薄い箔であっても高い立方体方位占有率を得ることができる。圧延ロールに接触しない面をつくりだすには、例えばいわゆる合わせ圧延（併せ圧延）を行うことが好ましい。すなわち、箔を２枚又はそれ以上重ね合わせた状態で圧延することにより、圧延ロールに接触しない面を有する薄箔を得ることができる。この場合、最終的に得られる薄箔の厚みを均一化するために、箔を重ね合わせる場合の総厚みは３５０μｍ以下とすることが好ましい。重ね合わせた箔の分離は、次の工程である焼鈍の前及び／又は後に実施することができる。この合わせ圧延においても、圧延ロールの平均粗度Ｒａを０．２５μｍ以下、特に０．２０μｍ以下、さらには０．１８μｍ以下とすることが好ましい。 In the present invention, when a thin foil is obtained by rolling a thick foil, it is preferable to perform rolling while ensuring a surface that does not contact the rolling roll. By securing a surface that does not come into contact with the rolling roll, it is possible to eliminate a factor that hinders the movement of crystal grains, and thereby a high cube orientation occupation ratio can be obtained even with a thin foil. In order to produce a surface that does not come into contact with the rolling roll, for example, it is preferable to perform so-called combined rolling (combined rolling). That is, the thin foil which has a surface which does not contact a rolling roll can be obtained by rolling in the state which piled up two or more foils. In this case, in order to make the thickness of the thin foil finally obtained uniform, the total thickness when the foils are overlapped is preferably 350 μm or less. Separation of the laminated foils can be carried out before and / or after the next step, annealing. Also in this combined rolling, it is preferable that the average roughness Ra of the rolling roll is 0.25 μm or less, particularly 0.20 μm or less, and further 0.18 μm or less.
上記の冷間圧延を実施した後、必要に応じて、中間焼鈍として１５０〜３５０℃（特に１５０〜３００℃）で１〜３０時間程度の熱処理を施すことが好ましい。特に前記の熱処理温度は３５０℃以下とすることが望ましい。熱処理温度を３５０℃以下とすることによって、５０μｍ以下の箔に圧延して焼鈍した後により高い立方体方位占有率を得ることができる。なお、中間焼鈍の雰囲気は限定的でなく、例えば真空中、大気中、不活性ガス雰囲気中等のいずれであっても良い。 After carrying out the above-described cold rolling, it is preferable to perform heat treatment at 150 to 350 ° C. (especially 150 to 300 ° C.) for about 1 to 30 hours as intermediate annealing, if necessary. In particular, the heat treatment temperature is desirably 350 ° C. or lower. By setting the heat treatment temperature to 350 ° C. or lower, a higher cube orientation occupation ratio can be obtained after rolling and annealing to a foil of 50 μm or less. The atmosphere of the intermediate annealing is not limited, and may be any of, for example, vacuum, air, inert gas atmosphere, and the like.
次に、前記薄箔をさらに冷間圧延することにより所望の箔厚みをもつ最終箔（最終的な箔厚みをもつ箔）を得る。すなわち、この冷間圧延によって、箔厚み５０μｍ以下の箔を得ることができる。なお、この冷間圧延においても、圧延ロールの平均粗度Ｒａを０．２５μｍ以下、特に０．２０μｍ以下、さらには０．１８μｍ以下とすることが好ましい。 Next, the thin foil is further cold-rolled to obtain a final foil having a desired foil thickness (a foil having a final foil thickness). That is, a foil having a thickness of 50 μm or less can be obtained by this cold rolling. In this cold rolling as well, the average roughness Ra of the rolling roll is preferably 0.25 μm or less, particularly 0.20 μm or less, and further preferably 0.18 μm or less.
本発明では、前記の最終箔に対して焼鈍（最終焼鈍）工程を実施することが好ましい。また、焼鈍工程に先立ち、例えば箔表面の圧延油、不純物、酸化皮膜を除去する等の目的で箔洗浄を行っても良い。洗浄後には乾燥を適宜行っても良い。特に、圧延油が過大に付着したまま高温の焼鈍を行なうと、箔表面の一部がシミ状に黄変し、エッチング処理を行なっても所望の形状のエッチングピットが得られなくなるおそれがある。 In this invention, it is preferable to implement an annealing (final annealing) process with respect to the said last foil. Prior to the annealing step, the foil may be washed for the purpose of removing rolling oil, impurities and oxide film on the foil surface, for example. You may dry suitably after washing | cleaning. In particular, if high-temperature annealing is performed with excessively applied rolling oil, a part of the foil surface is yellowed in a spot shape, and etching pits having a desired shape may not be obtained even if etching is performed.
焼鈍温度は限定的ではないが、通常４５０℃以上とし、特に４５０℃以上６６０℃未満、さらには５００〜６２０℃に設定することが望ましい。焼鈍温度が４５０℃未満になると立方体方位率が低下し、エッチング処理を行っても所望の形状のエッチングピットが得られなくなるおそれがある。焼鈍時間は、焼鈍温度等にもよるが、一般的には１〜１００時間程度とすれば良い。 The annealing temperature is not limited, but is usually 450 ° C. or higher, preferably 450 ° C. or higher and lower than 660 ° C., more preferably 500 to 620 ° C. When the annealing temperature is lower than 450 ° C., the cube orientation ratio is lowered, and there is a possibility that etching pits having a desired shape cannot be obtained even if etching is performed. The annealing time is generally about 1 to 100 hours, although it depends on the annealing temperature.
焼鈍雰囲気は、実質的に真空又は不活性ガス雰囲気とすることが望ましい。ただし、昇温及び降温の工程も含め３５０℃を超える場合には、焼鈍雰囲気中の酸素濃度を工業的に可能な限り低減させることが望ましい。すなわち、１０−５Ｔｏｒｒ以下の減圧下又は酸素を０〜１体積％含む不活性ガス雰囲気とすることが望ましい。１０−５Ｔｏｒｒを超える真空雰囲気又は焼鈍雰囲気中の酸素濃度が１．０体積％を超える不活性ガス雰囲気の場合は、焼鈍後の箔表面の一部がシミ状に黄変し、エッチング処理を行なっても所望の形状のエッチングピットが得られなくなるおそれがある。焼鈍雰囲気中の酸素濃度を上記のように設定することによって、薄くて均一な熱酸化皮膜が得られ、透気度の制御に寄与することができる。 The annealing atmosphere is desirably substantially a vacuum or an inert gas atmosphere. However, when the temperature exceeds 350 ° C. including the temperature raising and lowering steps, it is desirable to reduce the oxygen concentration in the annealing atmosphere as much as possible industrially. That is, it is desirable to set it as the inert gas atmosphere which contains 10 to 1 volume% of oxygen under the pressure reduction below 10 < -5 > Torr. In the case of an inert gas atmosphere in which the oxygen concentration in the vacuum atmosphere or annealing atmosphere exceeding 10 −5 Torr exceeds 1.0% by volume, a part of the foil surface after annealing turns yellow into a spot shape, and etching treatment is performed. Even if it carries out, there exists a possibility that the etching pit of a desired shape may no longer be obtained. By setting the oxygen concentration in the annealing atmosphere as described above, a thin and uniform thermal oxide film can be obtained, which can contribute to the control of the air permeability.
このようにして得られた箔（最終箔）に対してエッチング処理を施すことにより貫通孔を形成させる。エッチング処理の方法は限定的ではなく、１段階のエッチングにより所望の貫通孔を形成しても良いし、２段階又はそれ以上に分けて実施しても良い。 Through-holes are formed by subjecting the foil (final foil) thus obtained to an etching process. The method for the etching treatment is not limited, and a desired through hole may be formed by one-stage etching, or may be performed in two stages or more.
本発明では、例えば少なくとも２段階のエッチングとし、１段目のエッチングで貫通孔を形成し、２段目のエッチングで貫通孔の内径を調整することにより、所望の貫通孔を好適に形成することができる。 In the present invention, for example, a desired through hole is suitably formed by forming at least two stages of etching and forming a through hole by the first stage etching and adjusting the inner diameter of the through hole by the second stage etching. Can do.
この場合、１段目のエッチングは、好ましくは塩酸を主成分とする電解液中で直流エッチングする。１段目エッチングでは、主にエッチングピットを形成するとともにその密度と形状（貫通形状）を制御することができる。電解液としては、塩酸１〜１０重量％が水に溶解した水溶液を使用することができる。この場合、電解液中にはシュウ酸、リン酸、硫酸等を０．００１〜０．１重量％加えても良い。また、液温は６０〜９０℃程度とし、電流密度は０．１〜０．５Ａ／ｃｍ２程度とする。エッチング方式は、直流エッチングとすることが好ましい。なお、エッチング時間は、箔厚、目標とする透気度等に応じて適宜設定することができる。 In this case, the first-stage etching is preferably direct-current etching in an electrolyte containing hydrochloric acid as a main component. In the first stage etching, etching pits are mainly formed and the density and shape (through shape) can be controlled. As the electrolytic solution, an aqueous solution in which 1 to 10% by weight of hydrochloric acid is dissolved in water can be used. In this case, 0.001 to 0.1% by weight of oxalic acid, phosphoric acid, sulfuric acid or the like may be added to the electrolytic solution. The liquid temperature is about 60 to 90 ° C., and the current density is about 0.1 to 0.5 A / cm 2 . The etching method is preferably direct current etching. The etching time can be appropriately set according to the foil thickness, the target air permeability, and the like.
２段目のエッチングでは、好ましくはケミカルエッチングを実施する。これにより、主としてエッチングピット径を制御することができる。例えば、上記１段目エッチングと同組成・温度の液中で、ケミカルエッチングを行うことができる。エッチング時間は、例えば箔厚、目標とする透気度等に応じて適宜設定することができる。また、必ずしも塩酸を主成分としなくても良く、硝酸を主成分とした電解液中でも良い。また、ケミカルエッチングでなく、電解エッチングとしても良い。さらに必要に応じて、ケミカルエッチングや電解エッチング、エッチング液組成を組み合わせて、「２段目のエッチング」をさらに多段化しても良い。 In the second stage etching, chemical etching is preferably performed. Thereby, the etching pit diameter can be mainly controlled. For example, chemical etching can be performed in a liquid having the same composition and temperature as the first-stage etching. The etching time can be appropriately set according to, for example, the foil thickness and the target air permeability. Further, it is not always necessary to use hydrochloric acid as a main component, and it may be an electrolyte containing nitric acid as a main component. Moreover, it is good also as electrolytic etching instead of chemical etching. Furthermore, if necessary, “second-stage etching” may be further multi-staged by combining chemical etching, electrolytic etching, and etching solution composition.
以上のようにして得られた原箔を用いて、本発明加工を実施する。すなわち、原箔に対して引張加工と曲げ加工とを同時に行う。この場合、原箔の箔厚みは、貫通孔が実質的に保持される限りは本発明加工後に多少変化していても良いが、特に箔厚みの変化率は５％以下、特に１％以下、さらには０％とすることが好ましい。すなわち、実質的に原箔の厚みを維持しながら原箔に対して引張加工と曲げ加工とを同時に行うことが最も好ましい。原箔の箔厚みが大幅に変化する（特に大幅に薄くなる）と、貫通孔が変形し、所望の透気度等が得られなくなるので、変化率は上記範囲内に制御する。 The processing according to the present invention is performed using the raw foil obtained as described above. That is, a tensile process and a bending process are simultaneously performed on the raw foil. In this case, the foil thickness of the original foil may be changed somewhat after the processing of the present invention as long as the through-hole is substantially retained. In particular, the rate of change of the foil thickness is 5% or less, particularly 1% or less, Furthermore, it is preferable to set it as 0%. That is, it is most preferable to perform the tensile process and the bending process on the original foil at the same time while substantially maintaining the thickness of the original foil. When the foil thickness of the original foil changes significantly (especially significantly), the through hole is deformed and the desired air permeability cannot be obtained, so the rate of change is controlled within the above range.
一般に、原箔は、エッチングピットを箔表面から内部に伸ばし反対面まで貫通させるため、エッチング前においてアルミニウム箔を熱処理（焼鈍）し、完全に再結晶させ、好ましくは１つの細結晶粒が箔断面を貫通することが必要である。このように再結晶させるとアルミニウム箔の強度は著しく低下し、薄い箔に加工した場合のハンドリング性が悪くなる。本発明では、エッチングして貫通性を付与した原箔に引張加工と曲げ加工とを同時に行うことにより、耐力値を高めハンドリング性を良くし、箔切れやシワ発生を抑制することができる。ちなみに、前記の熱処理は４００℃以上の高温で実施する必要があるので、一般的にはエッチング前のアルミニウム箔の破断強度は約５０Ｎ／ｍｍ２以下、耐力値は約２０Ｎ／ｍｍ２以下になる。これらの数値の低下については、例えば、Ｆｅ、Ｓｉ、Ｃｕ等の元素添加（合金化）による強度改善も考えられるが、これらの元素はエッチング性を阻害するために多量には添加できず、実際上は合金化による強度改善は難しい。これに対し、本発明加工によれば、エッチング後の原箔に軽度の加工を施すことにより、透気度等に影響を及ぼすことなく強度を改善することができる。すなわち、軽度の引っ張り加工と曲げ加工を同時に行い、加工歪を導入することにより、耐力値を高めることができる。薄箔のハンドリング性はこの耐力値によりほぼ決定されることから、耐力値を高めることによりハンドリング性を向上させることができる。 In general, since the original foil extends the etching pits from the foil surface to the inside and penetrates to the opposite surface, the aluminum foil is heat-treated (annealed) and completely recrystallized before etching, and preferably one fine crystal grain has a cross section of the foil. It is necessary to penetrate. When recrystallized in this way, the strength of the aluminum foil is remarkably lowered, and the handleability when processed into a thin foil is deteriorated. In the present invention, by performing the tensile process and the bending process simultaneously on the original foil that has been etched and imparted with penetrability, the yield strength value can be increased, the handling property can be improved, and foil breakage and wrinkle generation can be suppressed. Incidentally, since it is necessary to carry out the heat treatment at a high temperature of 400 ° C. or higher, generally, the fracture strength of the aluminum foil before etching is about 50 N / mm 2 or less, and the proof stress value is about 20 N / mm 2 or less. . As for the decrease in these numerical values, for example, improvement in strength by adding (alloying) elements such as Fe, Si, Cu, etc. can be considered, but these elements cannot be added in large amounts because they hinder etching properties, and in fact, Above, it is difficult to improve the strength by alloying. On the other hand, according to the processing of the present invention, the strength can be improved without affecting the air permeability or the like by applying a slight processing to the original foil after etching. That is, the proof stress value can be increased by simultaneously performing a light pulling process and a bending process and introducing a processing strain. Since the handleability of the thin foil is almost determined by this yield strength value, the handleability can be improved by increasing the yield strength value.
引張加工と曲げ加工とを同時に行う方法は特に制限されず、公知の加工方法（加工装置）を単独又は組合せて用いることができる。例えば、プレス装置による加工、圧延装置による加工、ストレッチャーによる加工等を挙げることができる。これらの方法を用いて、原箔の箔厚みを監視しながらその加工レベルを調節すれば良い。この場合、強度の加工を行うと所望の透気度等が得られなくなるので、軽度のレベルで調整することが好ましい。 The method of performing the tensile process and the bending process at the same time is not particularly limited, and a known processing method (processing apparatus) can be used alone or in combination. For example, the process by a press apparatus, the process by a rolling apparatus, the process by a stretcher, etc. can be mentioned. Using these methods, the processing level may be adjusted while monitoring the foil thickness of the original foil. In this case, since the desired air permeability cannot be obtained when the strength is processed, it is preferable to adjust at a light level.
特に、本発明加工では、テンションレベラーによる加工を採用することが好ましい。テンションレベラーによる場合は、容易かつ確実に、貫通孔を変形させずに箔のタルミ形状をフラットに維持することができるので、本発明加工に最適な方法である。 In particular, in the processing according to the present invention, it is preferable to employ processing using a tension leveler. In the case of using a tension leveler, it is possible to easily and surely maintain the flat shape of the foil without deforming the through-hole, and this is an optimum method for the processing according to the present invention.
テンションレベラー自体は、公知又は市販のものを使用することができる。例えば、図３に示すように、原箔２０を巻いているローラー２１と巻き取り用ローラー２２との間に引張矯正及び曲げ矯正を行うための矯正用ローラー２３ａ〜２３ｉが配置された装置である。一般的には、前記の巻き取り用ローラーが駆動ローラーとなる。原箔２０を矯正用ローラーの間に通して適度な張力をかけることで均一な歪を付与し、加工硬化を促進することにより、所定の特性を付与することができる。矯正用ローラーの数、各ローラーの直径、位置（高低差、水平方向の間隔）等は適宜調整することができる。特に、テンションレベラーのユニット張力（すなわち、巻き取り用ローラー２２及び巻き戻し用ローラー２１における張力）を調整することにより、所定の特性を付与することができる。ユニット張力は、用いる原箔の特性（箔厚み、透気度等）、所望の耐力値等により適宜変更することができるが、通常は１〜２０Ｎ／１０ｍｍの範囲内とすれば良い。 A known or commercially available tension leveler can be used. For example, as shown in FIG. 3, correction rollers 23a to 23i for performing tension correction and bending correction are arranged between a roller 21 winding the raw foil 20 and a winding roller 22. . Generally, the winding roller is a driving roller. By passing the raw foil 20 between the correction rollers and applying an appropriate tension, uniform strain is imparted, and work hardening is promoted, thereby imparting predetermined characteristics. The number of rollers for correction, the diameter of each roller, the position (level difference, horizontal spacing), etc. can be adjusted as appropriate. In particular, by adjusting the unit tension of the tension leveler (that is, the tension in the take-up roller 22 and the rewind roller 21), predetermined characteristics can be imparted. The unit tension can be appropriately changed depending on the properties of the original foil to be used (foil thickness, air permeability, etc.), desired proof stress value, etc., but it is usually sufficient to be in the range of 1 to 20 N / 10 mm.
以下に実施例及び比較例を示し、本発明の特徴をより具体的に説明する。ただし、本発明の範囲は、実施例に限定されない。 The features of the present invention will be described more specifically with reference to the following examples and comparative examples. However, the scope of the present invention is not limited to the examples.
なお、各物性の測定方法は、次のようにして実施した。
（１）耐力値及び破断強度
ＪＩＳ Ｂ ７７２１に準じた引張試験機により引張試験を行なった。１０ｍｍ巾で長さ１５０ｍｍの試料を、チャック間距離が５０ｍｍとなるように固定し、引張速度１０ｍｍ／ｍｉｎで１０回測定し、その平均値を求めた。０．２％伸びの強度を耐力値とし、破断時の強度を破断強度とした。
In addition, the measuring method of each physical property was implemented as follows.
(1) Yield value and breaking strength A tensile test was performed with a tensile tester according to JIS B 7721. A sample having a width of 10 mm and a length of 150 mm was fixed so that the distance between chucks was 50 mm, measured 10 times at a tensile speed of 10 mm / min, and the average value was obtained. The strength at 0.2% elongation was taken as the proof stress value, and the strength at break was taken as the break strength.
（２）透気度
ＪＩＳ Ｐ ８１１７に準じたガーレ式デンソメータによる透気度試験方法によって測定する。
(2) Air permeability Measured by an air permeability test method using a Gurley type densometer according to JIS P 8117.
（３）シワ発生判定
活物質を塗工した際のシワの発生を次のように判定した。比表面積２０００ｍ２／ｇ平均粒径６μｍの活性炭を９０質量％及びＰＴＦＥ（ポリテトラフルオロエチレン）を１０質量％含む活物質をエタノールで混練したスラリー（固形分濃度３０％）を、図４に示すようにサポートロール（図４の２個のローラー）の間隔が２ｍの両面ダイコーターにより、乾燥後の塗布厚みが片面７０μｍとなるように塗工した。塗工速度は３ｍ／分とし、出側のサポートロール付近でのシワの発生を目視観察した。３５分間（約１００ｍ）観察し、シワの発生が全く認められなかったものを「○」、一度でも認められたものを「△」、頻繁に認められたものを「×」として評価した。
(3) Wrinkle generation determination The generation of wrinkles when an active material was applied was determined as follows. FIG. 4 shows a slurry (solid content concentration 30%) in which an active material containing 90% by mass of activated carbon having a specific surface area of 2000 m 2 / g and an average particle size of 6 μm and 10% by mass of PTFE (polytetrafluoroethylene) is kneaded with ethanol. Thus, the coating thickness after drying was applied by a double-sided die coater with a distance of 2 m between the support rolls (two rollers in FIG. 4) to be 70 μm on one side. The coating speed was 3 m / min, and the occurrence of wrinkles near the support roll on the exit side was visually observed. Observation was made for 35 minutes (about 100 m), and evaluation was made as “◯” when no wrinkle was observed, “Δ” when observed even once, and “×” when frequently observed.
（４）アルミニウム貫通箔（エッチング処理後）の垂直貫通孔占有率
エッチング処理後のアルミニウム貫通箔のＬＴ−ＳＴ面（圧延方向に垂直な断面）が観察面となるようにサンプル（１０ｍｍ幅）をエポキシ樹脂に埋め込み、試料をバフ研磨（ダイヤモンド研磨）する。その後、アルミニウム部分を電解（電解条件：エタノール：過塩素酸＝４：１の溶液にて、０℃、定電圧（２０Ｖ）電解×１８０秒）にて溶解し、エッチングピット（エッチングピットに入り込んだ樹脂部分）を走査型電子顕微鏡（ＳＥＭ）にて観察する。そして、無作為に撮影した１０視野（倍率５００倍）の写真から、図１に示すように各試料の測定長さが写真の寸法で１００ｍｍとなる部位を選び、図２に示すような角度測定用透明カードを上記写真に重ね合わせ、下表面から７０〜１１０°（９０±２０°）の範囲内の角度をもった貫通孔の数を計測し、全体の貫通孔の合計数を目視にてカウントした後、その合計数に対する割合を垂直貫通孔占有率（％）として算出する。
(4) Vertical through-hole occupancy of aluminum through-foil (after etching treatment) Sample (10 mm width) so that the LT-ST surface (cross section perpendicular to the rolling direction) of the aluminum through-foil after etching treatment becomes the observation surface The sample is embedded in an epoxy resin, and the sample is buffed (diamond polished). Thereafter, the aluminum part was dissolved by electrolysis (electrolysis condition: ethanol: perchloric acid = 4: 1 solution, 0 ° C., constant voltage (20 V) electrolysis × 180 seconds), and entered the etching pit (etching pit). The resin part) is observed with a scanning electron microscope (SEM). Then, from the photograph of 10 fields of view (500 times magnification) taken at random, the part where the measurement length of each sample is 100 mm in the dimension of the photograph is selected as shown in FIG. 1, and the angle measurement as shown in FIG. The transparent card for use is superimposed on the above photo, and the number of through holes with an angle in the range of 70 to 110 ° (90 ± 20 °) from the lower surface is measured, and the total number of all through holes is visually observed. After counting, the ratio to the total number is calculated as the vertical through-hole occupation ratio (%).
（５）貫通孔の内径
倍率を５０００倍としたほかは前記（１）と同様の方法にて無作為に１０視野の写真を撮影し、各試料の測定面積が写真の寸法で１００ｍｍ×１００ｍｍの範囲を画像解析してエッチングピット数及び総エッチングピット面積を計測し、貫通孔を円形と仮定して貫通孔の内径を算出する。画像解析装置としては、多目的高速画像解析装置「ＰＣＡ１１」（システムサイエンス株式会社製）を用いた。
(5) Inner diameter of the through-hole The photograph of 10 fields of view was taken at random by the same method as the above (1) except that the magnification was set to 5000 times, and the measurement area of each sample was 100 mm × 100 mm in the dimension of the photograph. The range is image-analyzed to measure the number of etching pits and the total etching pit area, and the inner diameter of the through hole is calculated assuming that the through hole is circular. As the image analysis apparatus, a multipurpose high-speed image analysis apparatus “PCA11” (manufactured by System Science Co., Ltd.) was used.
（６）表面積拡大比
エッチング処理後のアルミニウム貫通箔を６０℃の陽極酸化処理液（５％アジピン酸アンモニウム溶液）に浸漬し、１０Ｖで陽極酸化処理することにより陽極酸化皮膜を形成させた後、ＬＣＲメータを用いて静電容量を測定し、エッチング前のアルミニウム箔の静電容量比から算出する。測定投影面積は、５ｃｍ×１０ｃｍとした。
(6) Surface area expansion ratio After forming the anodic oxide film by immersing the aluminum penetration foil after the etching treatment in an anodizing solution (5% ammonium adipate solution) at 60 ° C. and anodizing at 10 V, The capacitance is measured using an LCR meter, and is calculated from the capacitance ratio of the aluminum foil before etching. The measurement projected area was 5 cm × 10 cm.
（７）貫通孔率
貫通孔率ｓ（％）＝［（１００×測定重量（ｇ））／（箔厚み（ｃｍ）×試料面積（ｃｍ２））］／（アルミニウムの比重（２．７０ｇ／ｃｍ３））を求めた。前記「箔厚み」は、試料４隅と中央部の計５点をマイクロメーターで測定した平均値とする。前記「試料面積」は１０ｃｍ×５ｃｍとする。前記「測定重量」は試料を電子天秤で秤量した値とする。
(7) Through Porosity Through Porosity s (%) = [(100 × Measured Weight (g)) / (Foil Thickness (cm) × Sample Area (cm 2 ))] / (Aluminum Specific Gravity (2.70 g / cm 3 )) was determined. The “foil thickness” is an average value obtained by measuring a total of five points at the four corners and the center of the sample with a micrometer. The “sample area” is 10 cm × 5 cm. The “measured weight” is a value obtained by weighing the sample with an electronic balance.
実施例１
Ｆｅ：１８重量ｐｐｍ、Ｓｉ：２０重量ｐｐｍ、Ｃｕ：２５ｐｐｍ、残部：Ａｌ及び不可避不純物からなる組成を有する溶湯を調製した後、溶湯を凝固させることにより鋳塊を得た。次いで、前記鋳塊を５００℃で１０時間の均質化処理を施した。その後、前記鋳塊に対して熱間圧延（温度４００℃）及び冷間圧延を施すことによって厚さ６５μｍまで圧延した。２５０℃で８時間の中間焼鈍を施した後、さらに冷間圧延を施すことによって厚さ５０μｍの箔を得た。有機溶剤系洗浄剤（イソプロピレン）で洗浄した後、アルゴンガス中で５００℃で１０時間の焼鈍した。次いで、塩酸５重量％を含む水溶液を電解液として用い、液温７０℃及び電流密度０．３Ａ／ｃｍ２で直流エッチングを行うことにより、貫通ピット（貫通孔）を多数有するアルミニウム貫通箔を得た。得られたアルミニウム貫通箔は、箔厚み：５０μｍ、耐力値：３．５Ｎ／１０ｍｍ、破断強度：１３．２Ｎ／１０ｍｍ、透気度：４２ｓｅｃ／１００ｍｌであった。
Example 1
After preparing a molten metal having a composition comprising Fe: 18 ppm by weight, Si: 20 ppm by weight, Cu: 25 ppm, the balance: Al and inevitable impurities, an ingot was obtained by solidifying the molten metal. Subsequently, the ingot was homogenized at 500 ° C. for 10 hours. Thereafter, the ingot was rolled to a thickness of 65 μm by hot rolling (temperature 400 ° C.) and cold rolling. After performing an intermediate annealing at 250 ° C. for 8 hours, a foil having a thickness of 50 μm was obtained by further cold rolling. After washing with an organic solvent-based cleaning agent (isopropylene), annealing was performed in argon gas at 500 ° C. for 10 hours. Next, using an aqueous solution containing 5% by weight of hydrochloric acid as an electrolytic solution, by performing direct current etching at a liquid temperature of 70 ° C. and a current density of 0.3 A / cm 2 , an aluminum through foil having a large number of through pits (through holes) is obtained. It was. The obtained aluminum penetration foil had a foil thickness of 50 μm, a proof stress value of 3.5 N / 10 mm, a breaking strength of 13.2 N / 10 mm, and an air permeability of 42 sec / 100 ml.
次に、上記アルミニウム貫通箔を原箔として用い、これをテンションレベラーにより加工を行った。テンションレベラーとしては、図３に示すように、９本のロールが上下方向に交互に配置されたものであり、各ロールはいずれも直径５０ｍｍである。ユニット張力は５Ｎ／１０ｍｍとした。加工処理が施されたＡｌ箔の箔厚み、［耐力値／破断強度］の値、透気度、活物質を塗工した際のシワ発生判定結果を表１に示し、垂直貫通孔占有率等を表２に示す。 Next, the said aluminum penetration foil was used as original foil, and this was processed with the tension leveler. As the tension leveler, as shown in FIG. 3, nine rolls are alternately arranged in the vertical direction, and each roll has a diameter of 50 mm. The unit tension was 5 N / 10 mm. Table 1 shows the thickness of the Al foil that has been processed, the value of [proof strength / breaking strength], the air permeability, and the wrinkle generation determination result when the active material is applied. Is shown in Table 2.
実施例２
テンションレベラーにより加工に際してユニット張力を８Ｎ／１０ｍｍとしたほかは、実施例１と同様にしてＡｌ箔を製造した。加工処理が施されたＡｌ箔の箔厚み、［耐力値／破断強度］の値、透気度及びシワ発生判定結果を表１に示し、垂直貫通孔占有率等を表２に示す。
Example 2
An Al foil was produced in the same manner as in Example 1 except that the unit tension was changed to 8 N / 10 mm during processing by the tension leveler. Table 1 shows the thickness of the Al foil subjected to the processing, the value of [proof strength / breaking strength], the air permeability, and the wrinkle generation determination result, and Table 2 shows the vertical through-hole occupation ratio and the like.
実施例３
実施例１と同様にして箔厚み３０μｍのアルミニウム貫通箔（原箔）を作製した。この箔は、耐力値：２．２Ｎ／１０ｍｍ、破断強度：８．２Ｎ／１０ｍｍ、透気度：３６ｓｅｃ／１００ｍｌであった。この原箔を用いて、テンションレベラーにより加工に際してユニット張力を３Ｎ／１０ｍｍとしたほかは、実施例１と同様にしてＡｌ箔を製造した。加工処理が施されたＡｌ箔の箔厚み、［耐力値／破断強度］の値、透気度及びシワ発生判定結果を表１に示し、垂直貫通孔占有率等を表２に示す。
Example 3
In the same manner as in Example 1, an aluminum penetrating foil (raw foil) having a foil thickness of 30 μm was produced. This foil had a proof stress value: 2.2 N / 10 mm, a breaking strength: 8.2 N / 10 mm, and an air permeability: 36 sec / 100 ml. Using this raw foil, an Al foil was produced in the same manner as in Example 1 except that the unit tension was changed to 3 N / 10 mm during processing by a tension leveler. Table 1 shows the thickness of the Al foil subjected to the processing, the value of [proof strength / breaking strength], the air permeability, and the wrinkle generation determination result, and Table 2 shows the vertical through-hole occupation ratio and the like.
実施例４
テンションレベラーにより加工に際してユニット張力を５Ｎ／１０ｍｍとしたほかは、実施例３と同様にしてＡｌ箔を製造した。加工処理が施されたＡｌ箔の箔厚み、［耐力値／破断強度］の値、透気度及びシワ発生判定結果を表１に示し、垂直貫通孔占有率等を表２に示す。
Example 4
An Al foil was produced in the same manner as in Example 3 except that the unit tension was changed to 5 N / 10 mm during processing by the tension leveler. Table 1 shows the thickness of the Al foil subjected to the processing, the value of [proof strength / breaking strength], the air permeability, and the wrinkle generation determination result, and Table 2 shows the vertical through-hole occupation ratio and the like.
実施例５
実施例１と同様にして箔厚み２０μｍのアルミニウム貫通箔（原箔）を作製した。この箔は、耐力値：２．１Ｎ／１０ｍｍ、破断強度：７．０Ｎ／１０ｍｍ、透気度：６５ｓｅｃ／１００ｍｌであった。この原箔を用いて、テンションレベラーにより加工に際してユニット張力を３Ｎ／１０ｍｍとしたほかは、実施例１と同様にしてＡｌ箔を製造した。加工処理が施されたＡｌ箔の箔厚み、［耐力値／破断強度］の値、透気度及びシワ発生判定結果を表１に示し、垂直貫通孔占有率等を表２に示す。
Example 5
In the same manner as in Example 1, an aluminum penetrating foil (raw foil) having a foil thickness of 20 μm was produced. This foil had a proof stress value: 2.1 N / 10 mm, a breaking strength: 7.0 N / 10 mm, and an air permeability: 65 sec / 100 ml. Using this raw foil, an Al foil was produced in the same manner as in Example 1 except that the unit tension was changed to 3 N / 10 mm during processing by a tension leveler. Table 1 shows the thickness of the Al foil subjected to the processing, the value of [proof strength / breaking strength], the air permeability, and the wrinkle generation determination result, and Table 2 shows the vertical through-hole occupation ratio and the like.
実施例６
テンションレベラーにより加工に際してユニット張力を５Ｎ／１０ｍｍとしたほかは、実施例５と同様にしてＡｌ箔を製造した。加工処理が施されたＡｌ箔の箔厚み、［耐力値／破断強度］の値、透気度及びシワ発生判定結果を表１に示し、垂直貫通孔占有率等を表２に示す。
Example 6
An Al foil was produced in the same manner as in Example 5 except that the unit tension was changed to 5 N / 10 mm during processing by the tension leveler. Table 1 shows the thickness of the Al foil subjected to the processing, the value of [proof strength / breaking strength], the air permeability, and the wrinkle generation determination result, and Table 2 shows the vertical through-hole occupation ratio and the like.
比較例１
実施例１及び２における原箔について、テンションレベラーにより加工を実施しなかったものについてのＡｌ箔の箔厚み、［耐力値／破断強度］の値、透気度及びシワ発生判定結果を表１に示し、垂直貫通孔占有率等を表２に示す。
Comparative Example 1
Table 1 shows the thickness of the Al foil, the value of [proof strength / breaking strength], the air permeability, and the wrinkle generation determination results of the raw foils in Examples 1 and 2 that were not processed by the tension leveler. Table 2 shows the vertical through-hole occupation ratio and the like.
比較例２
実施例３及び４における原箔について、テンションレベラーにより加工を実施しなかったものについてのＡｌ箔の箔厚み、［耐力値／破断強度］の値、透気度及びシワ発生判定結果を表１に示し、垂直貫通孔占有率等を表２に示す。
Comparative Example 2
Table 1 shows the thickness of the Al foil, the value of [proof strength / breaking strength], the air permeability, and the wrinkle generation determination results of the raw foils in Examples 3 and 4 that were not processed by the tension leveler. Table 2 shows the vertical through-hole occupation ratio and the like.
比較例３
実施例５及び６における原箔について、テンションレベラーにより加工を実施しなかったものについてのＡｌ箔の箔厚み、［耐力値／破断強度］の値、透気度及びシワ発生判定結果を表１に示し、垂直貫通孔占有率等を表２に示す。
Comparative Example 3
Table 1 shows the foil thickness of the Al foil, the value of [proof strength / breaking strength], the air permeability, and the wrinkle generation determination results for the raw foils in Examples 5 and 6 that were not processed by the tension leveler. Table 2 shows the vertical through-hole occupation ratio and the like.
Claims (6)
（１）箔厚みが５０μｍ以下であり、
（２）破断強度が［０．２×箔厚み（μｍ）］Ｎ／１０ｍｍ以上であり、
（３）［耐力値／破断強度］が５０％以上であり、
（４）Ｆｅ：５〜８０重量ｐｐｍ、Ｓｉ：５〜１００重量ｐｐｍ、Ｃｕ：１０〜１００重量ｐｐｍならびに残部：Ａｌ及び不可避不純物からなる組成を有する、
ことを特徴とする高強度アルミニウム貫通箔。 An aluminum through foil having a plurality of through holes from the foil surface to the back surface,
(1) The foil thickness is 50 μm or less,
(2) The breaking strength is [0.2 × foil thickness (μm)] N / 10 mm or more,
(3) [proof value / breaking strength] is 50% or more ,
(4) Fe: 5 to 80 ppm by weight, Si: 5 to 100 ppm by weight, Cu: 10 to 100 ppm by weight and the balance: Al and inevitable impurities,
A high-strength aluminum penetration foil characterized by that.
［０．１０×箔厚み（μｍ）］以上の値である、請求項１〜３のいずれかに記載の高強度アルミニウム貫通箔。 The surface area expansion ratio is
The high-strength aluminum penetrating foil according to any one of claims 1 to 3, which has a value equal to or greater than [0.10 × foil thickness (μm)].
高強度アルミニウム貫通箔が、
（１）箔厚みが５０μｍ以下であり、
（２）破断強度が［０．２×箔厚み（μｍ）］Ｎ／１０ｍｍ以上であり、
（３）［耐力値／破断強度］が５０％以上であり、
（４）Ｆｅ：５〜８０重量ｐｐｍ、Ｓｉ：５〜１００重量ｐｐｍ、Ｃｕ：１０〜１００重量ｐｐｍならびに残部：Ａｌ及び不可避不純物からなる組成を有する、
ことを特徴とする製造方法。
To aluminum penetration foil having a plurality of through holes extending from the foil surface on the back, I manufacturing method der high strength aluminum through foil which comprises a step of performing a tensile processing and bending at the same time,
High strength aluminum penetration foil
(1) The foil thickness is 50 μm or less,
(2) The breaking strength is [0.2 × foil thickness (μm)] N / 10 mm or more,
(3) [proof value / breaking strength] is 50% or more,
(4) Fe: 5 to 80 ppm by weight, Si: 5 to 100 ppm by weight, Cu: 10 to 100 ppm by weight and the balance: Al and inevitable impurities,
The manufacturing method characterized by the above-mentioned.
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| US13/499,130 US9331339B2 (en) | 2009-09-30 | 2010-09-22 | Perforated aluminium foil and manufacturing method thereof |
| CN201080043277.2A CN102575322B (en) | 2009-09-30 | 2010-09-22 | Perforated aluminum foil, and process for production thereof |
| PCT/JP2010/066358 WO2011040292A1 (en) | 2009-09-30 | 2010-09-22 | Perforated aluminum foil, and process for production thereof |
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| US9378897B2 (en) | 2011-05-26 | 2016-06-28 | Toyo Aluminium Kabushiki Kaisha | Electrode material for aluminum electrolytic capacitor, and process for producing same |
| JP5769528B2 (en) | 2011-07-15 | 2015-08-26 | 東洋アルミニウム株式会社 | Electrode material for aluminum electrolytic capacitor and method for producing the same |
| JP5945401B2 (en) * | 2011-11-24 | 2016-07-05 | 三菱アルミニウム株式会社 | Method for producing positive electrode current collector foil of lithium ion secondary battery |
| JP6073255B2 (en) | 2012-02-10 | 2017-02-01 | 東洋アルミニウム株式会社 | Method for producing electrode material for aluminum electrolytic capacitor |
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| JP5551300B1 (en) | 2013-10-30 | 2014-07-16 | 清二 加川 | Method for producing porous metal foil |
| JP6143946B2 (en) | 2014-04-10 | 2017-06-07 | 加川 清二 | Method and apparatus for producing microporous metal foil |
| TWI632726B (en) | 2014-10-21 | 2018-08-11 | 加川清二 | Method and apparatus for producing microporous metal foil |
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