JP5617611B2 - Composite metal foil with excellent tensile strength - Google Patents
Composite metal foil with excellent tensile strength Download PDFInfo
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- JP5617611B2 JP5617611B2 JP2010289691A JP2010289691A JP5617611B2 JP 5617611 B2 JP5617611 B2 JP 5617611B2 JP 2010289691 A JP2010289691 A JP 2010289691A JP 2010289691 A JP2010289691 A JP 2010289691A JP 5617611 B2 JP5617611 B2 JP 5617611B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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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、引張強度に優れる複合金属箔に関する。 The present invention relates to a composite metal foil excellent in tensile strength 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. 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、集電体への活物質の塗布は、集電体に高い張力をかけて行われる。また、活物質を塗布した集電体を巻き取る際、集電体には高い張力がかかる。従って、蓄電デバイスの正極集電体として用いるアルミニウム箔にはこうした張力に耐え得る引張強度を有することが求められる。しかしながら、アルミニウムは引張強度に優れる金属では必ずしもないので（現在、正極集電体として用いられている圧延アルミニウム箔の引張強度は１６０〜２３０Ｎ／ｍｍ２程度である）、蓄電デバイスの小型化や高エネルギー密度化のために箔の厚みを薄くしようとしても自ずと限界がある。そこでアルミニウム箔の引張強度を高める方法として、箔に鉄と珪素を微量添加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、この方法によっても、アルミニウム箔の引張強度が劇的に向上するわけではなく、また、この方法には、箔に添加した鉄や珪素が有機電解液中に溶出することによって電池特性に悪影響を及ぼす恐れがあるといった問題がある。 In manufacturing an electricity storage device, application of an active material to a current collector is performed by applying a high tension to the current collector. Further, when winding the current collector coated with the active material, a high tension is applied to the current collector. Therefore, the aluminum foil used as the positive electrode current collector of the electricity storage device is required to have a tensile strength that can withstand such tension. However, since aluminum is not necessarily a metal having excellent tensile strength (the tensile strength of rolled aluminum foil currently used as a positive electrode current collector is about 160 to 230 N / mm 2 ), it is possible to reduce the size and increase the power storage device. There is a limit to trying to reduce the thickness of the foil for energy density. Therefore, Patent Document 1 proposes a method of adding a small amount of iron and silicon to the foil as a method for increasing the tensile strength of the aluminum foil. However, this method does not dramatically improve the tensile strength of the aluminum foil, and this method has an adverse effect on battery characteristics due to the elution of iron or silicon added to the foil into the organic electrolyte. There is a problem that there is a risk of affecting.
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、引張強度に優れる複合金属箔を提供することを目的とする。 Then, an object of this invention is to provide the composite metal foil which can be used as a positive electrode electrical power collector etc. of an electrical storage device, and is excellent in tensile strength.
上記の点に鑑みてなされた本発明の複合金属箔は、請求項１記載の通り、アルミニウムよりも引張強度に優れる金属からなる箔の表面に、含水量が２０ｐｐｍ以下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記載の複合金属箔は、請求項１記載の複合金属箔において、アルミニウムよりも引張強度に優れる金属が、ニッケル、鉄、銅、チタン、これらの金属のうちの少なくとも１種を含む合金から選択されることを特徴とする。
また、請求項３記載の複合金属箔は、請求項１または２記載の複合金属箔において、電解法に用いる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記載の複合金属箔は、請求項３記載の複合金属箔において、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記載の複合金属箔は、請求項１乃至４のいずれかに記載の複合金属箔において、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、請求項６記載の複合金属箔は、請求項１乃至５のいずれかに記載の複合金属箔において、引張強度が３００Ｎ／ｍｍ２以上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７記載の通り、請求項１乃至６のいずれかに記載の複合金属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８記載の通り、請求項１乃至６のいずれかに記載の複合金属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９記載の通り、請求項８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 composite metal foil of the present invention made in view of the above points uses an electrolytic aluminum plating solution having a water content of 20 ppm or less on the surface of a foil made of a metal superior in tensile strength to aluminum as described in claim 1. An aluminum coating is formed by the conventional electrolytic method.
Moreover, the composite metal foil according to claim 2 is the composite metal foil according to claim 1, wherein the metal having higher tensile strength than aluminum is nickel, iron, copper, titanium, or at least one of these metals. It is selected from the alloy containing.
The composite metal foil according to claim 3 is the composite metal foil according to claim 1 or 2, wherein the electrolytic aluminum plating solution used in the electrolysis method 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 is the same or different, and contains at least one nitrogen-containing compound selected from the group consisting of quaternary ammonium salts represented by the following formula: And
The composite metal foil according to claim 4 is the composite metal foil according to claim 3, wherein the dialkyl sulfone is dimethyl sulfone.
The composite metal foil according to claim 5 is the composite metal foil according to any one of claims 1 to 4, wherein the film thickness of the aluminum coating is 1 to 50 μm.
The composite metal foil according to claim 6 is the composite metal foil according to any one of claims 1 to 5, wherein the tensile strength is 300 N / mm 2 or more.
Moreover, the positive electrode electrical power collector for electrical storage devices of this invention consists of the composite metal foil in any one of Claims 1 thru | or 6 as described in Claim 7.
The electrode for an electricity storage device of the present invention is characterized in that, as described in claim 8, an electrode active material is supported on the composite metal foil according to any one of claims 1 to 6.
Moreover, the electrical storage device of this invention is comprised using the electrode for electrical storage devices of Claim 8, as described in Claim 9. It is characterized by the above-mentioned.
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、引張強度に優れる複合金属箔を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the composite metal foil which can be used as a positive electrode electrical power collector of an electrical storage device etc. and is excellent in tensile strength can be provided.
本発明の複合金属箔は、アルミニウムよりも引張強度に優れる金属からなる箔の表面に、含水量が２０ｐｐｍ以下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、本発明は、アルミニウムよりも引張強度に優れる金属からなる箔を基材として用い、この箔の表面に電解法によってアルミニウム被膜を形成することで、引張強度に優れる複合金属箔を得るものである。 The composite metal foil of the present invention is characterized in that an aluminum film is formed on the surface of a foil made of a metal having a higher tensile strength than aluminum by an electrolytic method using an electrolytic aluminum plating solution having a water content of 20 ppm or less. To do. That is, the present invention provides a composite metal foil having an excellent tensile strength by using a foil made of a metal having an excellent tensile strength as compared with aluminum as a base material and forming an aluminum film on the surface of the foil by an electrolytic method. is there.
本発明において基材として用いるアルミニウムよりも引張強度に優れる金属からなる箔としては、例えばニッケル、鉄、銅、チタンなどの金属からなる箔が挙げられるが、これらの金属のうちの少なくとも１種を含む合金からなる箔、例えばニッケルと鉄の合金であるパーマロイからなる箔や、銅とベリリウムの合金からなる箔などでもよい。こうした箔は、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。電解法による金属箔の製造は、例えば所定の基材の表面に金属被膜を形成した後、当該被膜を基材から剥離して行うことができる。箔の厚みは、例えば５〜５０μｍであってよい。 Examples of the foil made of a metal superior in tensile strength to aluminum used as a substrate in the present invention include a foil made of a metal such as nickel, iron, copper, titanium, etc., and at least one of these metals is used. It may be a foil made of an alloy containing, for example, a foil made of permalloy, which is an alloy of nickel and iron, or a foil made of an alloy of copper and beryllium. Such a foil may be, for example, a commercially available foil manufactured by a rolling method, or may be manufactured by an electrolytic method. The production of the metal foil by the electrolytic method can be performed, for example, by forming a metal film on the surface of a predetermined substrate and then peeling the film from the substrate. The thickness of the foil may be 5 to 50 μm, for example.
基材として用いる箔の表面へのアルミニウム被膜の形成は、含水量が２０ｐｐｍ以下の電解アルミニウムめっき液を用いた電解法によって行う。電解法によれば、高純度で緻密なアルミニウム被膜を箔の表面に形成することができるので、ピンホールや無めっき部分の発生などの被膜の形成不良に起因して箔が有機電解液と接触することにより、箔を構成する金属が液中に溶出して電池特性に悪影響を及ぼすといった事態を防ぐことができる。めっき液の含水量を２０ｐｐｍ以下と規定するのは、めっき液の含水量が２０ｐｐｍを超えるとめっき液中の水分が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箔の表面に形成することができなくなる恐れがあるからである。めっき液の含水量を低減する方法としては、乾燥窒素ガスや乾燥アルゴンガスを用いてめっき液の構成成分となる物質に含まれる水分をパージしてからめっき液を調製する方法や、めっき液の構成成分となる物質を真空雰囲気中で乾燥してからめっき液を調製する方法などが挙げられる。 The formation of the aluminum film on the surface of the foil used as the substrate is performed by an electrolytic method using an electrolytic aluminum plating solution having a water content of 20 ppm or less. According to the electrolytic method, a high-purity and dense aluminum film can be formed on the surface of the foil, so that the foil is in contact with the organic electrolyte due to film formation defects such as pinholes and unplated parts. By doing so, it is possible to prevent a situation in which the metal constituting the foil elutes into the liquid and adversely affects the battery characteristics. The reason why the water content of the plating solution is defined as 20 ppm or less is that when the water content of the plating solution exceeds 20 ppm, moisture in the plating solution inhibits the precipitation of aluminum, and a uniform aluminum film is formed on the surface of the foil. Because there is a risk that it will be impossible. As a method of reducing the water content of the plating solution, a method of preparing a plating solution after purging moisture contained in a material constituting the plating solution using dry nitrogen gas or dry argon gas, For example, a method of preparing a plating solution after drying a constituent material in a vacuum atmosphere.
なお、基材として用いる箔とアルミニウム被膜の密着性を向上させるために、箔を構成する金属に応じた表面処理を箔に対して前処理として行ってもよい。こうした表面処理としては、例えばエッチング処理やストライクめっき処理や化成処理などが挙げられる。 In addition, in order to improve the adhesiveness of the foil used as a base material and an aluminum film, you may perform the surface treatment according to the metal which comprises foil as pre-processing with respect to foil. Examples of such surface treatment include etching treatment, strike plating treatment, and chemical conversion treatment.
本発明の引張強度に優れる複合金属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、基材として用いる箔の表面に形成するアルミニウム被膜の膜厚は、例えば１〜５０μｍが望ましいが、基材として用いる箔の厚みと合わせた複合金属箔の厚みが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を下回るとピンホールや無めっき部分の発生などの被膜の形成不良が起こりやすくなる恐れがある一方、膜厚が５０μｍを超えると複合金属箔が厚くなりすぎて集電体として用いることが困難になる恐れがある。 When it is assumed that the composite metal foil having excellent tensile strength of the present invention is used as a positive electrode current collector for an electricity storage device, the film thickness of the aluminum coating formed on the surface of the foil used as the substrate is preferably 1 to 50 μm, for example. The thickness of the composite metal foil combined with the thickness of the foil used as the substrate is more preferably 50 μm or less, and more preferably 30 μm or less. If the film thickness is less than 1 μm, film formation defects such as pinholes and unplated portions may occur easily. On the other hand, if the film thickness exceeds 50 μm, the composite metal foil becomes too thick and is used as a current collector. Can be difficult.
本発明において電解法に用いる電解アルミニウムめっき液は、基材として用いる箔の表面に電解法によって高純度で緻密な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で緻密なアルミニウム被膜を基材として用いる箔の表面に形成することができる。 The electrolytic aluminum plating solution used in the electrolysis method in the present invention is not particularly limited as long as it can form a high-purity and dense aluminum film on the surface of the foil used as the base material by electrolysis. It may be a known one including a plating solution composed 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: If this plating solution is used, it can be formed on the surface of a foil that uses a high-purity and dense aluminum coating rich in ductility at a high film formation rate 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が、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。 Examples of the aluminum halide include aluminum chloride and aluminum bromide, but 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 halide is preferably anhydrous.
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で緻密な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 and dense 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１〜２０Ａ／ｄｍ２の条件下、基材として用いるアルミニウムよりも引張強度に優れる金属からなる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用いる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１Ａ／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で緻密な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 superior in tensile strength to aluminum used as a base material, for example, under conditions where the temperature of the plating solution is 80 to 110 ° C. and the applied current density is 1 to 20 A / dm 2. A foil made of metal may be used as a cathode (aluminum may 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 foil used as the substrate and the plating solution is activated, and the purity is obtained by incorporating a large amount of impurities into the aluminum coating. May decrease. On the other hand, when the applied current density is less than 1 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 cannot be performed due to decomposition of a nitrogen-containing compound or the like. There is a risk that a high-purity and dense aluminum coating rich in quality 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複合金属箔は、基材としてアルミニウムよりも引張強度に優れる金属からなる箔を用いているので、例えば３００Ｎ／ｍｍ２以上の優れた引張強度を有するとともに、その表面に高純度で緻密なアルミニウム被膜が形成されているので、有機電解液中において安定に存在することができることから、蓄電デバイス用正極集電体として有用である。 Since the composite metal foil of the present invention produced as described above uses a foil made of a metal superior in tensile strength to aluminum as a base material, it has excellent tensile strength of, for example, 300 N / mm 2 or more. Since a high-purity and dense aluminum coating film is formed on the surface thereof, it can be stably present in the organic electrolyte, and thus is useful as a positive electrode current collector for an electricity storage device.
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：
厚みが２５μｍの市販の圧延アルミニウム箔（日本製箔社製）の引張強度を測定したところ、２１０Ｎ／ｍｍ２であった（島津製作所社製の精密万能試験機：ＥＺＴｅｓｔを用いて測定、以下同じ）。
Reference example 1:
When the tensile strength of a commercially available rolled aluminum foil (manufactured by Nippon Foil Co., Ltd.) having a thickness of 25 μm was measured, it was 210 N / mm 2 (measured using a precision universal testing machine manufactured by Shimadzu Corporation: EZTest, the same applies hereinafter) ).
実施例１：
ジメチルスルホン：無水塩化アルミニウム：トリメチルアミン塩酸塩をモル比で１０：３：０．０５の割合で混合した後、２４時間、乾燥窒素ガスを用いて水分をパージしてから、１１０℃で溶解させて電解アルミニウムめっき液を調製した。こうして調製されためっき液の含水量は５ｐｐｍであった（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２０μｍの市販の圧延ニッケル箔（ニラコ社製）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５分間行い、圧延ニッケル箔の表面に膜厚が５μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は均一かつ平滑で、ピンホールの発生などの形成不良は認められなかった（顕微鏡観察による、以下同じ）。こうして得られた複合金属箔の引張強度は４２０Ｎ／ｍｍ２であった。
Example 1:
After mixing dimethylsulfone: anhydrous aluminum chloride: trimethylamine hydrochloride in a molar ratio of 10: 3: 0.05, the water was purged with dry nitrogen gas for 24 hours and then dissolved at 110 ° C. An electrolytic aluminum plating solution was prepared. The water content of the plating solution thus prepared was 5 ppm (measured using a trace moisture measuring device manufactured by Mitsubishi Chemical Corporation: CA-100, the same applies hereinafter). Using this plating solution, an aluminum plate having a purity of 99.99 mass% was used for the anode, and a commercially available rolled nickel foil (made by Niraco) having a thickness of 20 μm was used for the cathode, and the plating solution was applied at an applied current density of 5 A / dm 2. The electroplating treatment was performed for 5 minutes while stirring at a stirring speed of 300 rpm while maintaining the temperature at 95 ° C. to form an aluminum film having a thickness of 5 μm on the surface of the rolled nickel foil. The surface of the aluminum coating was uniform and smooth, and formation defects such as pinholes were not observed (the same applies to the following by microscopic observation). The composite metal foil thus obtained had a tensile strength of 420 N / mm 2 .
実施例２：
ジメチルスルホン：無水塩化アルミニウム：トリメチルアミン塩酸塩：塩化テトラメチルアンモニウムをモル比で１０：３：０．０５：１の割合で混合した後、２４時間、乾燥窒素ガスを用いて水分をパージしてから、１１０℃で溶解させて電解アルミニウムめっき液を調製した。こうして調製されためっき液の含水量は２０ｐｐｍであった。このめっき液を用いて、陽極に純度９９．９９ｍａｓｓ％のアルミニウム板、陰極に厚みが２０μｍの市販の圧延ニッケル箔（ニラコ社製）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５０分間行い、圧延ニッケル箔の表面に膜厚が４８μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は均一かつ平滑で、ピンホールの発生などの形成不良は認められなかった。こうして得られた複合金属箔の引張強度は４３１Ｎ／ｍｍ２であった。
Example 2:
After mixing dimethylsulfone: anhydrous aluminum chloride: trimethylamine hydrochloride: tetramethylammonium chloride in a molar ratio of 10: 3: 0.05: 1, the moisture was purged with dry nitrogen gas for 24 hours. The electrolytic aluminum plating solution was prepared by dissolving at 110 ° C. The water content of the plating solution thus prepared was 20 ppm. Using this plating solution, an aluminum plate having a purity of 99.99 mass% was used for the anode, and a commercially available rolled nickel foil (made by Niraco) having a thickness of 20 μm was used for the cathode, and the plating solution was applied at an applied current density of 5 A / dm 2. Electroplating treatment was performed for 50 minutes while stirring at a stirring speed of 300 rpm while maintaining the temperature at 95 ° C. to form an aluminum film having a thickness of 48 μm on the surface of the rolled nickel foil. The surface of the aluminum coating was uniform and smooth, and no formation defects such as pinholes were found. The composite metal foil thus obtained had a tensile strength of 431 N / mm 2 .
実施例３：
１５Ａ／ｄｍ２の印加電流密度で電気めっき処理を２分間行うこと以外は実施例１と同様にして、圧延ニッケル箔の表面に膜厚が４μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は均一かつ平滑で、ピンホールの発生などの形成不良は認められなかった。こうして得られた複合金属箔の引張強度は４２５Ｎ／ｍｍ２であった。
Example 3:
An aluminum coating having a thickness of 4 μm was formed on the surface of the rolled nickel foil in the same manner as in Example 1 except that the electroplating treatment was performed for 2 minutes at an applied current density of 15 A / dm 2 . The surface of the aluminum coating was uniform and smooth, and no formation defects such as pinholes were found. The composite metal foil thus obtained had a tensile strength of 425 N / mm 2 .
実施例４：
１．５Ａ／ｄｍ２の印加電流密度で電気めっき処理を５０分間行うこと以外は実施例１と同様にして、圧延ニッケル箔の表面に膜厚が１５μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は均一かつ平滑で、ピンホールの発生などの形成不良は認められなかった。こうして得られた複合金属箔の引張強度は４２１Ｎ／ｍｍ２であった。
Example 4:
An aluminum film having a film thickness of 15 μm was formed on the surface of the rolled nickel foil in the same manner as in Example 1 except that the electroplating treatment was performed at an applied current density of 1.5 A / dm 2 for 50 minutes. The surface of the aluminum coating was uniform and smooth, and no formation defects such as pinholes were found. The composite metal foil thus obtained had a tensile strength of 421 N / mm 2 .
実施例５：
市販のニッケルめっき液（ＮＩ−ＳＴＫ：ワールドメタル社製）を用いたストライクニッケルめっき処理を行った厚みが２０μｍの市販の圧延ステンレス箔（ニラコ社製）を陰極に用いること以外は実施例１と同様にして、ストライクニッケルめっき処理を行った圧延ステンレス箔の表面に膜厚が５μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は均一かつ平滑で、ピンホールの発生などの形成不良は認められなかった。こうして得られた複合金属箔の引張強度は５２０Ｎ／ｍｍ２であった。
Example 5:
Example 1 except that a commercially available rolled stainless steel foil (manufactured by Niraco Co., Ltd.) having a thickness of 20 μm subjected to strike nickel plating using a commercially available nickel plating solution (NI-STK: manufactured by World Metal Co., Ltd.) is used as the cathode. Similarly, an aluminum film having a thickness of 5 μm was formed on the surface of the rolled stainless steel foil subjected to the strike nickel plating treatment. The surface of the aluminum coating was uniform and smooth, and no formation defects such as pinholes were found. The composite metal foil thus obtained had a tensile strength of 520 N / mm 2 .
実施例６：
厚みが１５μｍの市販の圧延ベリリウム銅箔（ニラコ社製）を陰極に用いること以外は実施例１と同様にして、圧延ベリリウム銅箔の表面に膜厚が５μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は均一かつ平滑で、ピンホールの発生などの形成不良は認められなかった。こうして得られた複合金属箔の引張強度は５４０Ｎ／ｍｍ２であった。
Example 6:
An aluminum film having a thickness of 5 μm was formed on the surface of the rolled beryllium copper foil in the same manner as in Example 1 except that a commercially available rolled beryllium copper foil (manufactured by Nilaco) having a thickness of 15 μm was used as the cathode. The surface of the aluminum coating was uniform and smooth, and no formation defects such as pinholes were found. The composite metal foil thus obtained had a tensile strength of 540 N / mm 2 .
実施例７：
乾燥窒素ガス雰囲気下で無水塩化アルミニウム：エチルメチルイミダゾリウムクロリドをモル比で６７：３３の割合で混合した後、８０℃で溶解させて電解アルミニウムめっき液を調製した。こうして調製されためっき液の含水量は１０ｐｐｍであった。このめっき液を用いて、陽極に純度９９．９９ｍａｓｓ％のアルミニウム板、陰極に厚みが２０μｍの市販の圧延ニッケル箔（ニラコ社製）を用い、２Ａ／ｄｍ２の印加電流密度で、めっき液を８０℃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２５分間行い、圧延ニッケル箔の表面に膜厚が１０μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は均一かつ平滑で、ピンホールの発生などの形成不良は認められなかった。こうして得られた複合金属箔の引張強度は４３０Ｎ／ｍｍ２であった。
Example 7:
Under a dry nitrogen gas atmosphere, anhydrous aluminum chloride: ethylmethylimidazolium chloride was mixed at a molar ratio of 67:33, and then dissolved at 80 ° C. to prepare an electrolytic aluminum plating solution. The water content of the plating solution thus prepared was 10 ppm. Using this plating solution, an aluminum plate having a purity of 99.99 mass% was used as the anode, and a commercially available rolled nickel foil (made by Nilaco) having a thickness of 20 μm was used as the cathode, and the plating solution was applied at an applied current density of 2 A / dm 2. The electroplating process was performed for 25 minutes while maintaining the temperature at 80 ° C. while stirring at a stirring speed of 300 rpm to form an aluminum film having a thickness of 10 μm on the surface of the rolled nickel foil. The surface of the aluminum coating was uniform and smooth, and no formation defects such as pinholes were found. The composite metal foil thus obtained had a tensile strength of 430 N / mm 2 .
実施例８：
厚みが２０μｍの市販の圧延パーマロイ箔（ニラコ社製）を陰極に用いること以外は実施例１と同様にして、圧延パーマロイ箔の表面に膜厚が５μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は均一かつ平滑で、ピンホールの発生などの形成不良は認められなかった。こうして得られた複合金属箔の引張強度は６３０Ｎ／ｍｍ２であった。
この複合金属箔を試験極、リチウム箔を対極及び参照極とし、電解液に１Ｍ ＬｉＰＦ６／ＥＣ＋ＤＭＣを用いて擬似電池セルを作製した。電気化学測定装置（ＨＺ−５０００：北斗電工社製）を用いてこの擬似電池セルでサイクリックボルタンメトリーを３サイクル行い、その特性を電気化学的に評価した。結果を図１に示す。図１から明らかなように、この複合金属箔を試験極とした場合、１サイクル目においては、４〜６Ｖの領域で表面のアルミニウム被膜の不働態化に伴う酸化反応が観察されたが、２サイクル目からは安定した挙動を示し、基材として用いた圧延パーマロイ箔の腐食に伴うニッケルや鉄の溶出を示す酸化反応は観察されなかった。以上の結果から、この複合金属箔は、引張強度に優れる蓄電デバイス用正極集電体として好適に利用できることがわかった。
Example 8:
An aluminum film having a thickness of 5 μm was formed on the surface of the rolled permalloy foil in the same manner as in Example 1 except that a commercially available rolled permalloy foil (manufactured by Nilaco) having a thickness of 20 μm was used as the cathode. The surface of the aluminum coating was uniform and smooth, and no formation defects such as pinholes were found. The composite metal foil thus obtained had a tensile strength of 630 N / mm 2 .
The composite metal foil was used as a test electrode, the lithium foil was used as a counter electrode and a reference electrode, and a pseudo battery cell was produced using 1M LiPF 6 / EC + DMC as an electrolyte. Using an electrochemical measurement device (HZ-5000: manufactured by Hokuto Denko Co., Ltd.), cyclic voltammetry was performed for 3 cycles in this pseudo battery cell, and the characteristics were evaluated electrochemically. The results are shown in FIG. As can be seen from FIG. 1, when this composite metal foil was used as a test electrode, in the first cycle, an oxidation reaction accompanying passivation of the surface aluminum coating was observed in the region of 4 to 6 V. From the cycle, stable behavior was observed, and no oxidation reaction showing elution of nickel or iron accompanying corrosion of the rolled permalloy foil used as the substrate was observed. From the above results, it was found that this composite metal foil can be suitably used as a positive electrode current collector for an electricity storage device having excellent tensile strength.
比較例１：
厚みが２５μｍの市販の圧延チタン箔（ニラコ社製）の引張強度を測定したところ、７３０Ｎ／ｍｍ２であった。
この圧延チタン箔を試験極とすること以外は実施例８と同様にして擬似電池セルを作製し、その特性を電気化学的に評価した。結果を図２に示す。図２から明らかなように、この圧延チタン箔を試験極とした場合、圧延チタン箔の継続的な腐食に伴うチタンの溶出よって３サイクル目においても４〜６Ｖの領域で酸化反応が観察されたことから、この圧延チタン箔は蓄電デバイス用正極集電体として利用できないことがわかった。
Comparative Example 1:
It was 730 N / mm < 2 > when the tensile strength of the commercially available rolled titanium foil (made by Nilaco) whose thickness is 25 micrometers was measured.
A pseudo battery cell was produced in the same manner as in Example 8 except that this rolled titanium foil was used as a test electrode, and its characteristics were electrochemically evaluated. The results are shown in FIG. As is clear from FIG. 2, when this rolled titanium foil was used as a test electrode, an oxidation reaction was observed in the region of 4 to 6 V even in the third cycle due to elution of titanium accompanying continuous corrosion of the rolled titanium foil. This indicates that this rolled titanium foil cannot be used as a positive electrode current collector for an electricity storage device.
比較例２：
水を添加して含水量を５０ｐｐｍに調整した電解アルミニウムめっき液を用いること以外は実施例１と同様にして、圧延ニッケル箔の表面に膜厚が５μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は凹凸が激しく、無数のピンホールが認められた。この複合金属箔を試験極とすること以外は実施例８と同様にして擬似電池セルを作製し、その特性を電気化学的に評価したところ、基材として用いた圧延ニッケル箔がピンホールを通して電解液と接触したことでその継続的な腐食に伴うニッケルの溶出よって３サイクル目においても４〜６Ｖの領域で酸化反応が観察されたことから、この複合金属箔は蓄電デバイス用正極集電体として利用できないことがわかった。
Comparative Example 2:
An aluminum film having a thickness of 5 μm was formed on the surface of the rolled nickel foil in the same manner as in Example 1 except that an electrolytic aluminum plating solution whose water content was adjusted to 50 ppm by adding water was used. The surface of the aluminum coating was very uneven, and numerous pinholes were observed. A pseudo battery cell was produced in the same manner as in Example 8 except that this composite metal foil was used as a test electrode, and its characteristics were evaluated electrochemically. As a result, the rolled nickel foil used as a substrate was electrolyzed through a pinhole. Since the oxidation reaction was observed in the region of 4 to 6 V even in the third cycle due to the elution of nickel accompanying the continuous corrosion due to contact with the liquid, this composite metal foil was used as a positive electrode current collector for power storage devices. I found that it was not available.
比較例３：
厚みが１５μｍの市販の圧延ベリリウム銅箔（ニラコ社製）を陰極に用いること以外は比較例２と同様にして、圧延ベリリウム銅箔の表面に膜厚が５μｍのアルミニウム被膜を形成した。アルミニウム被膜の表面は凹凸が激しく、無数のピンホールが認められた。この複合金属箔を試験極とすること以外は実施例８と同様にして擬似電池セルを作製し、その特性を電気化学的に評価したところ、基材として用いた圧延ベリリウム銅箔がピンホールを通して電解液と接触したことでその継続的な腐食に伴う銅の溶出よって３サイクル目においても４〜６Ｖの領域で酸化反応が観察されたことから、この複合金属箔は蓄電デバイス用正極集電体として利用できないことがわかった。
Comparative Example 3:
An aluminum film having a thickness of 5 μm was formed on the surface of the rolled beryllium copper foil in the same manner as in Comparative Example 2 except that a commercially available rolled beryllium copper foil (manufactured by Niraco) having a thickness of 15 μm was used as the cathode. The surface of the aluminum coating was very uneven, and numerous pinholes were observed. A pseudo battery cell was prepared in the same manner as in Example 8 except that this composite metal foil was used as a test electrode, and its characteristics were evaluated electrochemically. The rolled beryllium copper foil used as the base material passed through the pinhole. This composite metal foil is a positive electrode current collector for an electricity storage device because an oxidation reaction was observed in the region of 4 to 6 V even in the third cycle due to elution of copper accompanying continuous corrosion due to contact with the electrolyte. As it turned out that it is not available.
応用例１：本発明の引張強度に優れる複合金属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で得た複合金属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 composite metal foil excellent in tensile strength of the present invention as a positive electrode current collector for an electricity storage device The composite metal foil obtained in Example 1 was used as a positive electrode current collector, and the surface thereof was used. An electricity storage device having a configuration known per se was produced using the positive electrode active material applied as the 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、引張強度に優れる複合金属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。
INDUSTRIAL APPLICABILITY The present invention has industrial applicability in that it can provide a composite metal foil having excellent tensile strength that can be used as a positive electrode current collector of an electricity storage device.
Claims (9)
A power storage device comprising the power storage device electrode according to claim 8.
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| JP2014075205A (en) * | 2012-10-03 | 2014-04-24 | Hitachi Metals Ltd | Power storage device |
| JP5709024B2 (en) * | 2012-12-17 | 2015-04-30 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery and current collector for secondary battery |
| US9947917B2 (en) * | 2013-10-25 | 2018-04-17 | Uacj Corporation | Aluminum alloy foil for current collector of electrode, and manufacturing method thereof |
| US10581081B1 (en) | 2019-02-01 | 2020-03-03 | Chang Chun Petrochemical Co., Ltd. | Copper foil for negative electrode current collector of lithium ion secondary battery |
| CN114792807B (en) * | 2022-04-20 | 2023-10-27 | 江阴纳力新材料科技有限公司 | Positive electrode lithium-rich composite current collector and preparation method thereof |
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