JPWO2014178327A1 - Copper foil for negative electrode current collector of lithium ion secondary battery - Google Patents

Copper foil for negative electrode current collector of lithium ion secondary battery Download PDF

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JPWO2014178327A1
JPWO2014178327A1 JP2014531014A JP2014531014A JPWO2014178327A1 JP WO2014178327 A1 JPWO2014178327 A1 JP WO2014178327A1 JP 2014531014 A JP2014531014 A JP 2014531014A JP 2014531014 A JP2014531014 A JP 2014531014A JP WO2014178327 A1 JPWO2014178327 A1 JP WO2014178327A1
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copper foil
negative electrode
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secondary battery
lithium ion
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JP5625141B1 (en
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隆宏 鶴田
隆宏 鶴田
健作 篠崎
健作 篠崎
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

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Abstract

銅箔（集電体）と活物質との密着性と銅箔の防錆性を改良し、リチウムイオン二次電池負極集電体用電解銅箔、並びに、該銅箔を負極集電体としたリチウムイオン二次電池を提供する。銅箔は、当該銅箔中に含まれる不純物である炭素、硫黄、酸素、窒素、塩素の含有量の合計が２０ｐｐｍ以下、より好ましくは１０ｐｐｍ以下であり、かつ、ＸＰＳ（Ｘ線光電子分光分析）により窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上２．０ｎｍ未満、より好ましくは０．２ｎｍ以上１．０ｎｍ以下である。当該銅箔は、銅箔表面に有機防錆皮膜が形成され、ＮＭＰ（Ｎ−メチルピロリドン）接触角が１５°以下である。Improvement in adhesion between copper foil (current collector) and active material and rust prevention of copper foil, electrolytic copper foil for negative electrode current collector of lithium ion secondary battery, and copper foil as negative electrode current collector Provided is a lithium ion secondary battery. The copper foil has a total content of carbon, sulfur, oxygen, nitrogen, and chlorine, which are impurities contained in the copper foil, of 20 ppm or less, more preferably 10 ppm or less, and XPS (X-ray photoelectron spectroscopy). The depth range that is detected to be greater than the background level of nitrogen and carbon is 0.2 nm or more and less than 2.0 nm, more preferably 0.2 nm or more and 1.0 nm or less. The copper foil has an organic rust preventive film formed on the surface of the copper foil and an NMP (N-methylpyrrolidone) contact angle of 15 ° or less.

Description

本発明はリチウムイオン二次電池負極集電体用銅箔に関するものである。
より特定的には、本発明は、銅箔表面に、有機防錆皮膜が形成されているリチウムイオン二次電池負極集電体用銅箔に関する。The present invention relates to a copper foil for a negative electrode current collector of a lithium ion secondary battery.
More specifically, this invention relates to the copper foil for lithium ion secondary battery negative electrode electrical power collectors in which the organic rust preventive film is formed in the copper foil surface.

リチウムイオン二次電池はエネルギー密度が高く、比較的高い電圧を得ることができるという特徴を有し、たとえば、ノートパソコン、ビデオカメラ、デジタルカメラ、携帯電話等の小型電子機器の電源として多用されている。また、たとえば、電気自動車や一般家庭の分散配置型電源といった大型機器の電源としての利用も始まっている。
このように、リチウムイオン二次電池は、他の二次電池と比較して軽量でエネルギー密度が高いことから、各種の電源を必要とする機器で広く使用されている。Lithium ion secondary batteries are characterized by high energy density and the ability to obtain relatively high voltages. For example, they are frequently used as power sources for small electronic devices such as notebook computers, video cameras, digital cameras, and mobile phones. Yes. Also, for example, use as a power source for large equipment such as an electric vehicle and a distributed power source for general households has begun.
Thus, lithium ion secondary batteries are widely used in devices that require various power sources because they are lighter and have a higher energy density than other secondary batteries.

リチウムイオン二次電池の負極用集電体として使用される銅箔に要求される特性の一つとして、リチウムイオン二次電池のサイクル特性に影響する負極活物質との密着性が挙げられる。
銅箔表面との密着性に劣る活物質層では、銅箔をサイジングしたり、折り曲げたり、巻回した場合に活物質層が剥離、脱落して、目的の性能が得られず、耐久性や寿命が低下する場合がある。
また、活物質層の厚みの均一性が不十分に形成されると、その部分でリチウム析出・デンドライト発生が生じ、短絡が生じやすくなり、短時間での充電が困難となる。One of the characteristics required for a copper foil used as a negative electrode current collector of a lithium ion secondary battery is adhesion to a negative electrode active material that affects the cycle characteristics of the lithium ion secondary battery.
In an active material layer with poor adhesion to the copper foil surface, when the copper foil is sized, bent, or wound, the active material layer peels off and falls off, and the desired performance cannot be obtained. Life may be reduced.
In addition, when the thickness of the active material layer is insufficiently uniform, lithium deposition and dendrite are generated at the portion, short circuit is likely to occur, and charging in a short time becomes difficult.

活物質層との密着性を改善するための一般的な方法としては、銅箔表面を粗化処理し、物理的に改善する方法、あるいは、銅箔表面を防錆し、シランカップリング層を設けて化学的に改善する方法等がある。   As a general method for improving the adhesion with the active material layer, the surface of the copper foil is roughened and physically improved, or the surface of the copper foil is rust-prevented and a silane coupling layer is formed. There is a method of providing and improving chemically.

特許文献１（特開２０１２−２１２５２８号公報）は、負極活物質との接着性、超音波溶接性、防錆性がバランス良く向上した二次電池負極集電体用電解銅箔として、銅箔表面の少なくとも一部にアゾール系化合物及びＣ＝Ｏを有する表面処理層が形成され、ＸＰＳ（Ｘ線光電子分光分析）による深さ方向分析で、窒素（Ｎ）及び炭素（Ｃ）を検出し、且つ、Ｎ及びＣ検出量がバックグラウンドレベルよりも大きい深さ範囲の平均値Ｄ0が２．０〜５．０ｎｍであるリチウムイオン二次電池負極集電体用電解銅箔を開示する。
しかし、特許文献１に開示されているリチウムイオン二次電池負極集電体用電解銅箔では銅箔に含まれる不可避的不純物の全体の含有量についての解析が行われておらず、僅かに窒素（Ｎ）と炭素（Ｃ）についてのみ問題視しており、他の不純物、たとえば、硫黄（Ｓ）、酸素（Ｏ）、塩素（Ｃｌ）については追及していない。Patent Document 1 (Japanese Patent Application Laid-Open No. 2012-212528) discloses a copper foil as an electrolytic copper foil for a secondary battery negative electrode current collector with improved balance of adhesion to a negative electrode active material, ultrasonic weldability, and rust prevention. A surface treatment layer having an azole compound and C═O is formed on at least a part of the surface, and nitrogen (N) and carbon (C) are detected by depth direction analysis by XPS (X-ray photoelectron spectroscopy), and, N and C detect the amount of average D 0 larger depth range than the background level discloses a lithium ion secondary battery negative electrode current collector electrolytic copper foil is 2.0～5.0Nm.
However, the electrolytic copper foil for a negative electrode current collector of a lithium ion secondary battery disclosed in Patent Document 1 has not been analyzed for the total content of inevitable impurities contained in the copper foil, and is slightly nitrogenous. Only (N) and carbon (C) are considered as problems, and other impurities such as sulfur (S), oxygen (O), and chlorine (Cl) are not pursued.

また、リチウムイオン二次電池の負極電極は、活物質材料と結着剤を溶媒と混合して得られる活物質スラリーペーストを導電性担体（銅箔等）に塗布後、乾燥し、そして、密度を上げる必要があればプレスして結着させて活物質層を形成する。上記銅箔の表面には、アゾール系誘導体を用いる有機防錆処理又はクロム化合物系の溶液を用いるクロメート処理で防錆加工されている。   In addition, the negative electrode of the lithium ion secondary battery is coated with an active material slurry paste obtained by mixing an active material and a binder with a solvent on a conductive carrier (copper foil, etc.), then dried, and the density If necessary, the active material layer is formed by pressing and binding. The surface of the copper foil is rustproofed by an organic rustproofing treatment using an azole derivative or a chromate treatment using a chromium compound solution.

前記ペーストを形成する溶媒には、一般に、Ｎ−メチルピロリドン（ＮＭＰ）、水等が使用されている。
しかしながら、溶媒に水を用いるとバインダーとのわずかな混合比の違いで電池特性が変化する等の問題がある。
一方、ＮＭＰは、沸点（２０２℃）が比較的低いため回収して再利用しやすく、カルボニル基を有する非プロトン性極性溶媒であるため高い溶解性を持ち、様々な溶媒と混ざり合うことができるため好ましく使用されている。しかし、負極電極の担体となる銅箔はＮＭＰとの濡れ性が悪く、厚塗りする等の特別な対策を必要としている。In general, N-methylpyrrolidone (NMP), water, or the like is used as a solvent for forming the paste.
However, when water is used as a solvent, there is a problem that battery characteristics change due to a slight difference in mixing ratio with the binder.
NMP, on the other hand, has a relatively low boiling point (202 ° C.), so it can be easily recovered and reused, and since it is an aprotic polar solvent having a carbonyl group, it has high solubility and can be mixed with various solvents. Therefore, it is preferably used. However, the copper foil serving as the negative electrode carrier has poor wettability with NMP and requires special measures such as thick coating.

上記ペーストに含まれる活物質材料や、バインダーは、銅表面との親和力に乏しく密着性が低い。
銅箔表面との密着性に劣る活物質層で構成した負極電極では、電極をサイジングしたり、折り曲げたり、巻回しした場合に活物質層が剥離、脱落して、目的の性能が得られず、耐久性や寿命に問題が発生する。
前述したように活物質膜の厚みが不均一で厚さの薄い層が形成されると、その部分でリチウム析出・デンドライト発生が生じ、短絡が生じやすくなるため、短時間での充電が困難となる。The active material and binder contained in the paste have poor affinity with the copper surface and low adhesion.
In a negative electrode composed of an active material layer with poor adhesion to the copper foil surface, the active material layer peels off and falls off when the electrode is sized, bent, or wound, and the desired performance cannot be obtained. Problems with durability and lifetime.
As described above, when the active material film has a non-uniform thickness and a thin layer is formed, lithium deposition and dendrite are generated at that portion, and a short circuit is likely to occur. Become.

特許文献２（特開２００８−２５１４６９号公報）は、このような銅箔と活物質との密着性を改善する方法として、銅箔表面に、カルボニル基を有するアゾール化合物を含有する皮膜を形成し、ＮＭＰ接触角を１９°以下とした銅箔を開示する。
特許文献２には、９９．９０％以上のタフピッチ銅を用いた圧延銅箔を、イソプロピルアルコールやノルマルパラフィン、またはこれらの混合液へ所定量のカルボキシベンゾトリアゾールを添加した溶液へ５秒間浸漬した後、送風乾燥させ、更にモノエチルアミン又は１，２，３ベンゾトリアゾールを添加して同様に処理することが記載されている。
しかし、特許文献２にも、銅箔に含まれる不可避的不純物についての解析は記載されておらず、不可避的不純物による銅箔表面の濡れ性については追及されていない。つまり、特許文献２に記載の銅箔では、銅箔に含まれる不可避的不純物の全体量が多い場合には、銅箔と活物質層と濡れ性が悪く、集電体としての機能を満足できない場合がある点については検討されていない。Patent Document 2 (Japanese Unexamined Patent Application Publication No. 2008-251469) discloses a method for improving the adhesion between the copper foil and the active material by forming a film containing an azole compound having a carbonyl group on the surface of the copper foil. The copper foil which made NMP contact angle 19 degrees or less is disclosed.
In Patent Document 2, a rolled copper foil using 99.90% or more of tough pitch copper is immersed for 5 seconds in a solution obtained by adding a predetermined amount of carboxybenzotriazole to isopropyl alcohol, normal paraffin, or a mixture thereof. It is described that it is blown and dried, and further treated with monoethylamine or 1,2,3 benzotriazole.
However, Patent Document 2 also does not describe analysis of inevitable impurities contained in the copper foil, and does not pursue the wettability of the copper foil surface by inevitable impurities. That is, in the copper foil described in Patent Document 2, when the total amount of inevitable impurities contained in the copper foil is large, the wettability between the copper foil and the active material layer is poor, and the function as a current collector cannot be satisfied. There are no considerations for possible cases.

特開２０１２−２１２５２８号公報JP 2012-212528 A 特開２００８−２５１４６９号公報JP 2008-251469 A

本発明者は、リチウムイオン二次電池の負極集電体として使用される銅箔の活物質との密着性及び防錆性向上につき鋭意研究開発を行った結果、銅箔に含まれる不純物である炭素（Ｃ）、硫黄（Ｓ）、酸素（Ｏ）、窒素（Ｎ）、塩素（Ｃｌ）の量、および、防錆皮膜の厚さが、集電体（銅箔）と活物質層との密着性に大きく影響することを突き止め、本発明を完成させた。   This inventor is an impurity contained in copper foil as a result of earnest research and development about the adhesiveness with the active material of copper foil used as a negative electrode collector of a lithium ion secondary battery, and rust prevention improvement. The amount of carbon (C), sulfur (S), oxygen (O), nitrogen (N), chlorine (Cl), and the thickness of the rust preventive film are determined by the current collector (copper foil) and the active material layer. The inventors have found out that the adhesiveness is greatly affected and completed the present invention.

本発明は、銅箔と活物質との密着性と銅箔の防錆性を改良し、リチウムイオン二次電池負極集電体用表面処理銅箔、並びに、該表面処理銅箔を集電体としたリチウムイオン二次電池を提供することにある。   The present invention improves the adhesion between a copper foil and an active material and the rust preventive property of the copper foil, the surface-treated copper foil for a negative electrode current collector of a lithium ion secondary battery, and the surface-treated copper foil as a current collector It is to provide a lithium ion secondary battery.

本発明のリチウムイオン二次電池負極集電体用表面処理銅箔は、銅箔中に含まれる炭素、硫黄、酸素、窒素、塩素の含有量の合計が２０ｐｐｍ以下であり、かつ、ＸＰＳ（Ｘ線光電子分光分析）により窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上２．０ｎｍ未満であることを特徴とする。
なお、リチウムイオン二次電池負極集電体用銅箔は、電解銅箔、電解銅合金箔及び圧延銅箔及び圧延銅合金箔のいずれかを含む。The surface-treated copper foil for the negative electrode current collector of the lithium ion secondary battery of the present invention has a total content of carbon, sulfur, oxygen, nitrogen and chlorine contained in the copper foil of 20 ppm or less, and XPS (X The depth range which is detected to be larger than the background level of nitrogen and carbon by linear photoelectron spectroscopy is 0.2 nm or more and less than 2.0 nm.
In addition, the copper foil for lithium ion secondary battery negative electrode collectors includes any one of an electrolytic copper foil, an electrolytic copper alloy foil, a rolled copper foil, and a rolled copper alloy foil.

すなわち、前記銅箔中に含まれる炭素、硫黄、酸素、窒素、塩素の含有量の合計は２０ｐｐｍ以下であり、特に好ましくは１０ｐｐｍ以下である。   That is, the total content of carbon, sulfur, oxygen, nitrogen and chlorine contained in the copper foil is 20 ppm or less, particularly preferably 10 ppm or less.

また、好ましくは、前記ＸＰＳ（Ｘ線光電子分光分析）により窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲は０．２ｎｍ以上２．０ｎｍ未満であり、特に好ましくは、０．２ｎｍ以上１．０ｎｍ以下である。   Preferably, the depth range detected by the XPS (X-ray photoelectron spectroscopy) to be larger than the background level of nitrogen and carbon is 0.2 nm or more and less than 2.0 nm, and particularly preferably 0.2 nm. It is 1.0 nm or less.

本発明に係る銅箔によれば、該銅箔を集電体とすることで負極活物質との接着性が向上する。
その結果、本発明の銅箔を、たとえば、リチウムイオン二次電池の集電体として好適に使用することができる。According to the copper foil which concerns on this invention, adhesiveness with a negative electrode active material improves by using this copper foil as a collector.
As a result, the copper foil of this invention can be used conveniently as a collector of a lithium ion secondary battery, for example.

以下、本発明の実施形態につき詳細に説明する。
本発明のリチウムイオン二次電池負極集電体用銅箔は、銅箔中に含まれる炭素、硫黄、酸素、窒素、塩素の含有量の合計が２０ｐｐｍ以下であり、かつ、ＸＰＳにより窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上２．０ｎｍ未満であることを特徴とする。Hereinafter, embodiments of the present invention will be described in detail.
The copper foil for the negative electrode current collector of the lithium ion secondary battery of the present invention has a total content of carbon, sulfur, oxygen, nitrogen and chlorine contained in the copper foil of 20 ppm or less, and nitrogen and carbon by XPS. The depth range that is detected to be larger than the background level is 0.2 nm or more and less than 2.0 nm.

（銅箔基材）
本発明において、「銅箔」は、電解銅箔、電解銅合金箔及び圧延銅箔及び圧延銅合金箔のいずれでもよい。以下でこれらの銅箔を区別する必要がない時は単に「銅箔」と表現する。(Copper foil base material)
In the present invention, the “copper foil” may be any of an electrolytic copper foil, an electrolytic copper alloy foil, a rolled copper foil, and a rolled copper alloy foil. Hereinafter, when it is not necessary to distinguish these copper foils, they are simply expressed as “copper foils”.

銅箔にはその製箔工程の如何に係らず炭素（Ｃ）、硫黄（Ｓ）、酸素（Ｏ）、窒素 （Ｎ）、塩素（Ｃｌ）の全てが、或いはその一部が不可避的不純物として含まれる。
この不純物の量が多くなると、銅箔表面に塗布する有機防錆皮膜との間で濡れ性が悪くなり、防錆皮膜を均一に塗布することが困難となる。
本実施形態では、銅箔の表面に必要により粗化処理を施し、その上に有機防錆皮膜を塗布する。In copper foil, carbon (C), sulfur (S), oxygen (O), nitrogen (N), chlorine (Cl), or a part of it as an unavoidable impurity, regardless of the foil production process included.
When the amount of this impurity increases, the wettability with the organic rust preventive film applied to the copper foil surface deteriorates, and it becomes difficult to uniformly apply the rust preventive film.
In this embodiment, the surface of the copper foil is roughened as necessary, and an organic rust preventive film is applied thereon.

本発明のリチウムイオン二次電池負極集電体用銅箔に要求される特性の一つに活物質層との密着性がある。本実施形態のリチウムイオン二次電池の負極電極は、活物質、たとえば、カーボン材料と結着剤を溶媒とともに混合した活物質スラリーペーストを集電体（銅箔）に塗布後、乾燥し、密度を上げる必要があればプレスして結着させて活物質層を形成する。このとき、ペーストを作製する溶媒にＮＭＰ（Ｎ−メチルピロリドン）を使用した活物質スラリーペーストと銅箔表面との密着性が問題となる。   One of the characteristics required for the copper foil for a negative electrode current collector of the lithium ion secondary battery of the present invention is adhesion to the active material layer. The negative electrode of the lithium ion secondary battery of the present embodiment is coated with an active material, for example, an active material slurry paste in which a carbon material and a binder are mixed with a solvent, and then dried on a current collector (copper foil). If necessary, the active material layer is formed by pressing and binding. At this time, the adhesiveness between the active material slurry paste using NMP (N-methylpyrrolidone) as a solvent for preparing the paste and the copper foil surface becomes a problem.

本実施形態の集電体用銅箔において、銅箔中に含まれる不純物の量を規定している。特に、不純物であるＣ、Ｓ、Ｏ、Ｎ、Ｃｌ（以下、これらを単に不可避的不純物と表現する場合がある。）の含有量の合計を２０ｐｐｍ以下とする。
メカニズムは完全に解明されていないが、銅箔に含まれる不可避的不純物の量を２０ｐｐｍ以下とするのは、不可避的不純物が２０ｐｐｍ以上含有すると、銅箔内部の不可避的不純物の元素と、活物質スラリーペーストに含まれるＮＭＰなどの有機溶媒との間で電気的な斥力が生じ、活物質スラリーペーストに対する銅箔の表面張力が大きくなるために活物質スラリーペーストとの濡れ性が悪く、リチウムイオン二次電池の負極として仕上げた際の集電体と活物質層との密着性が悪くなる、と考えられる。
不可避的不純物の含有量は、少ないほうが良いが、許容値としては、好ましくは１５ｐｐｍ以下、更に好ましくは１０ｐｐｍ以下である。In the copper foil for current collectors of this embodiment, the amount of impurities contained in the copper foil is defined. In particular, the total content of impurities C, S, O, N, and Cl (hereinafter sometimes simply referred to as inevitable impurities) is set to 20 ppm or less.
Although the mechanism is not completely elucidated, the amount of inevitable impurities contained in the copper foil is set to 20 ppm or less. When the inevitable impurities are contained in an amount of 20 ppm or more, the elements of the inevitable impurities in the copper foil and the active material An electrical repulsive force is generated with an organic solvent such as NMP contained in the slurry paste, and the surface tension of the copper foil with respect to the active material slurry paste is increased. It is considered that the adhesion between the current collector and the active material layer when finished as the negative electrode of the secondary battery is deteriorated.
The content of inevitable impurities is preferably as low as possible, but the allowable value is preferably 15 ppm or less, more preferably 10 ppm or less.

本実施形態の銅箔の有機防錆層は、ＸＰＳ（Ｘ線光電子分光分析）により窒素（Ｎ）および炭素（Ｃ）のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上２．０ｎｍ未満である。
本実施形態ではＸ線光電子分光分析装置（ＸＰＳ装置）とアルゴンスパッタとを組み合わせて、銅箔の深さ方向の元素分析を行い、有機防錆層の厚みを決定する。即ち、ＸＰＳ装置にて有機防錆層中のＮ及びＣを検出し、且つ、Ｎ及びＣ検出量がバックグラウンドレベルよりも大きい深さ範囲を表面処理層の厚みとする。
表面処理層の厚みは、密着性、防錆性の観点から０．２ｎｍ以上２．０ｎｍ未満とすることが好ましく、より好ましくは０．５ｎｍ以上１．０ｎｍ以下である。
表面処理層の厚みが２．０ｎｍ以上であると、防錆処理剤を塗布した後の乾燥工程などに防錆成分の一部が粉状となって表出し、活物質との密着性を損なうおそれがある。The organic rust prevention layer of the copper foil of the present embodiment has a depth range of 0.2 nm or more and 2 which is detected to be larger than the background level of nitrogen (N) and carbon (C) by XPS (X-ray photoelectron spectroscopy). Less than 0.0 nm.
In the present embodiment, the elemental analysis in the depth direction of the copper foil is performed by combining an X-ray photoelectron spectrometer (XPS apparatus) and argon sputtering, and the thickness of the organic rust preventive layer is determined. That is, N and C in the organic rust preventive layer are detected by the XPS apparatus, and the depth range in which the detected amount of N and C is larger than the background level is set as the thickness of the surface treatment layer.
The thickness of the surface treatment layer is preferably 0.2 nm or more and less than 2.0 nm, more preferably 0.5 nm or more and 1.0 nm or less from the viewpoint of adhesion and rust prevention.
When the thickness of the surface treatment layer is 2.0 nm or more, a part of the rust preventive component appears as a powder in the drying process after applying the rust preventive agent, and the adhesion to the active material is impaired. There is a fear.

集電体（銅箔）に設ける活物質層の密着性を向上するためには銅箔表面に塗布する有機防錆皮膜の膜厚が均一であり、かつ密度の高い皮膜であることが好ましい。銅箔表面に、有機防錆皮膜付着量を均一に塗布する方法として、本実施形態では親水化ロールによる塗布方法を採用する。
銅箔表面に有機防錆皮膜を均一に塗布する方法としては、有機防錆処理液（例えばトリアゾール溶液）に浸漬され表面に有機防錆処理液が塗布された銅箔の表裏両面に、親水化ロールをセットし、該親水化ロールで銅箔表面に塗布された溶液が均一になるように均す（処理する）。
このように親水化ロールを使用することで銅箔表面に有機防錆剤を均一に塗布することができる。
銅箔表面に有機防錆剤を塗布する時に親水化ロールを使用することで、銅箔と処理液の接触時に、処理液の液滴がつぶれ、同じ付着量でも密度の高い有機防錆皮膜を形成することができるため、本発明のような薄い皮膜であっても、十分な防錆性能を発揮することができる。なお、密度が高く厚さの均一な有機防錆皮膜を形成できるのであれば、親水化ロールによる塗布以外の方法であってもよい。
また、このように親水化ロ−ルで皮膜を形成することで皮膜の厚さを均一にでき、銅箔表面の抵抗率を下げることができるため、負極電極を組み立てる際に抵抗溶接を行う場合でも、防錆皮膜におけるジュール熱の消費が抑制され、重ね合わせた箔の内部にジュール熱が適切に供給されることから、良好な抵抗溶接性が得られる。In order to improve the adhesion of the active material layer provided on the current collector (copper foil), it is preferable that the organic rust preventive film applied to the copper foil surface has a uniform film thickness and a high density. In the present embodiment, a coating method using a hydrophilic roll is adopted as a method for uniformly coating the surface of the copper foil with the organic rust preventive film adhesion amount.
As a method of uniformly applying an organic rust preventive coating on the surface of copper foil, the surface of both sides of the copper foil coated with the organic rust preventive treatment solution (for example, triazole solution) is hydrophilized. A roll is set, and the solution applied to the copper foil surface with the hydrophilizing roll is leveled (treated) so that the solution is uniform.
Thus, an organic rust preventive agent can be uniformly apply | coated to the copper foil surface by using a hydrophilization roll.
By using a hydrophilizing roll when applying an organic rust inhibitor to the copper foil surface, when the copper foil and the treatment liquid are in contact, the droplets of the treatment liquid are crushed. Since it can form, even if it is a thin film like this invention, sufficient rust prevention performance can be exhibited. In addition, as long as an organic rust preventive film having a high density and a uniform thickness can be formed, a method other than coating by a hydrophilic roll may be used.
In addition, when the film is formed with the hydrophilic roll in this way, the thickness of the film can be made uniform and the resistivity of the copper foil surface can be lowered, so that resistance welding is performed when the negative electrode is assembled. However, the consumption of Joule heat in the rust preventive film is suppressed, and Joule heat is appropriately supplied to the inside of the laminated foil, so that good resistance weldability can be obtained.

親水化ロールは、例えばゴムロールをＵＶオゾン処理、プラズマ処理、親水官能基による化学修飾等の手法でロール表面を親水化処理する。このようなロールを使用して有機防錆処理液を塗布することで、有機防錆剤付着量のバラツキが極めて少ない塗膜を形成することができる。   For example, the hydrophilizing roll hydrophilizes the roll surface by a technique such as UV ozone treatment, plasma treatment or chemical modification with a hydrophilic functional group. By applying the organic rust preventive treatment liquid using such a roll, it is possible to form a coating film with very little variation in the amount of organic rust preventive agent attached.

銅箔表面に有機防錆剤を親水化処理していないロールで塗布すると、銅箔と処理液の接触時、処理液の液滴のサイズが大きく、液滴内に処理液成分が拡散するため、均一に塗布することが難しくなり、単位面積当たり同じ付着量でもその中での付着量のバラツキが大きくなる場合がある。付着量のバラツキが大きい銅箔においては、皮膜の厚さが薄いところでは皮膜の一部に空孔（ピンホール）が発生して保管・輸送環境下で局所的な錆（点錆）が発生する惧れがあり、他方、厚く付着したところでは、皮膜の除去に必要となる熱や振動によるエネルギーが大きくなるため、後工程の負極電極を組み立てる超音波溶接に悪影響が生ずる惧れがある。   If an organic rust inhibitor is applied to the copper foil surface with a roll that has not been hydrophilized, the size of the treatment liquid droplets is large and the treatment liquid components diffuse into the droplets when the copper foil contacts the treatment liquid. It becomes difficult to apply uniformly, and even in the same amount of adhesion per unit area, the variation in the amount of adhesion may increase. In copper foil with a large variation in the amount of adhesion, when the film thickness is thin, holes (pinholes) are generated in a part of the film, and local rust (point rust) occurs in the storage / transport environment. On the other hand, when the film is thickly attached, the energy required for removing the film increases due to heat and vibration, which may adversely affect ultrasonic welding for assembling the negative electrode in the subsequent process.

有機防錆皮膜としては、ベンゾトリアゾール、トリルトリアゾール、カルボキシベンゾトリアゾール、クロロベンゾトリアゾール、エチルベンゾトリアゾール、ナフトトリアゾール等のトリアゾール化合物、およびこれらの錯体化合物が挙げられる。
銅箔表面に有機防錆皮膜を形成するトリアゾール系化合物、または／および、その錯体化合物からなる有機防錆化合物溶液（以下、トリアゾール化合物溶液と云うことがある）の濃度は、５０〜１０００ｐｐｍとすることが望ましい。５０ｐｐｍを下回ると防錆機能を保持できるほどの厚さの有機防錆皮膜とならず、他方、１０００ｐｐｍを超えると有機防錆皮膜の厚さが過剰に大きくなり、上記したように超音波溶接機能等に悪影響が生じる惧れがあるためである。Examples of the organic rust preventive film include triazole compounds such as benzotriazole, tolyltriazole, carboxybenzotriazole, chlorobenzotriazole, ethylbenzotriazole, and naphthotriazole, and complex compounds thereof.
The concentration of an organic rust-preventing compound solution (hereinafter sometimes referred to as a triazole compound solution) composed of a triazole-based compound that forms an organic rust-proof coating on the copper foil surface and / or a complex compound thereof is 50 to 1000 ppm. It is desirable. If it is less than 50 ppm, the organic rust preventive film is not thick enough to maintain the rust preventive function. On the other hand, if it exceeds 1000 ppm, the organic rust preventive film becomes excessively thick, and the ultrasonic welding function as described above. This is because there is a possibility that adverse effects may occur.

また、銅箔表面に有機防錆皮膜を形成する際のトリアゾール化合物溶液の温度は、３５℃〜５５℃とすることが望ましい。３５℃を下回ると、防錆機能を保持できるほどの密度の有機防錆皮膜とならず、他方、５５℃を上回ると有機防錆皮膜の密度が過剰に高くなるためである。
さらに、トリアゾール化合物溶液のｐＨはトリアゾール成分の安定性を確保するため、溶液のｐＨを６．５〜８．０とすることが好ましい。
銅箔に塗布するトリアゾール化合物溶液の濃度、溶液温度、ｐＨ等の条件、銅箔の浸漬時間等は形成する有機防錆皮膜の厚みとの関係で適宜に決めることができる。なお、浸漬時間は通常０．５〜３０秒程度であればよい。
ただし、これらの防錆処理条件に関する記述は例示であり、明細書・請求項の内容を拘束するものではない。Moreover, as for the temperature of the triazole compound solution at the time of forming an organic rust preventive film on the copper foil surface, it is desirable to set it as 35 to 55 degreeC. This is because when the temperature is lower than 35 ° C., the organic rust preventive film has a density sufficient to maintain the antirust function, and when the temperature is higher than 55 ° C., the density of the organic rust preventive film becomes excessively high.
Furthermore, the pH of the triazole compound solution is preferably 6.5 to 8.0 in order to ensure the stability of the triazole component.
Conditions such as the concentration of the triazole compound solution to be applied to the copper foil, the solution temperature, pH, the immersion time of the copper foil, and the like can be appropriately determined in relation to the thickness of the organic rust preventive film to be formed. In addition, immersion time should just be about 0.5-30 second normally.
However, the description regarding these rust prevention treatment conditions is an illustration, and does not restrain the content of a specification and a claim.

本実施形態においては、電解銅箔製箔後ただちに有機防錆剤溶液に浸漬して防錆皮膜を形成するが、製箔後ただちに防錆処理できない場合は、前処理として酸洗い、または脱脂を施す。
酸洗いをする場合は、Ｈ2ＳＯ4＝５〜２００ｇ／１（リットル）、温度＝１０℃〜８０℃の希硫酸に浸漬する酸洗い方法が効果的である。
また、脱脂の場合は、ＮａＯＨ＝５〜２００ｇ／１、温度＝１０℃〜８０℃の水溶液中で、電流密度＝１〜１０Ａ／ｄｍ2、０．１分〜５分で陰極又は／及び陽極電解脱脂を行うのが効果的である。In this embodiment, immediately after the electrolytic copper foil is made, it is immersed in an organic rust preventive solution to form a rust preventive film, but if the rust preventive treatment is not possible immediately after the foil is made, pickling or degreasing is performed as a pretreatment. Apply.
In the case of pickling, an acid pickling method of immersing in dilute sulfuric acid at H 2 SO 4 = 5 to 200 g / 1 (liter) and temperature = 10 ° C. to 80 ° C. is effective.
In the case of degreasing, the cathode or / and the anode in an aqueous solution of NaOH = 5 to 200 g / 1, temperature = 10 ° C. to 80 ° C., current density = 1-10 A / dm 2 , 0.1 min-5 min It is effective to perform electrolytic degreasing.

本実施形態では上記銅箔を集電体とし、その上に負極活物質層を形成して負極電極を作製し、該負極電極を組み込み、リチウムイオン二次電池を作製する。
負極活物質としては、限定的ではないが、炭素、珪素、スズ、ゲルマニウム、鉛、アンチモン、アルミニウム、インジウム、リチウム、酸化スズ、チタン酸リチウム、窒化リチウム、インジウムを固溶した酸化錫、インジウム−錫合金、リチウム−アルミニウム合金、リチウム−インジウム合金等が挙げられる。In this embodiment, the copper foil is used as a current collector, a negative electrode active material layer is formed thereon to produce a negative electrode, and the negative electrode is incorporated to produce a lithium ion secondary battery.
Examples of the negative electrode active material include, but are not limited to, carbon, silicon, tin, germanium, lead, antimony, aluminum, indium, lithium, tin oxide, lithium titanate, lithium nitride, indium-tin oxide, indium- Examples thereof include a tin alloy, a lithium-aluminum alloy, and a lithium-indium alloy.

以下、本発明を実施例１〜９、比較例１〜６により具体的に説明する。
〔銅箔の製箔〕
〔実施例１〜９〕
〔比較例１〜６〕
実施例１〜９および比較例１〜６は、次に示す条件で、アノードには貴金属酸化物被覆チタン電極、カソードにはチタン製回転ドラムを用いて、電流密度＝５０〜１００Ａ／ｄｍ2で、厚さ１０μｍの電解銅箔を製造した。
銅： ７０〜１３０ｇ／１
硫酸： ８０〜１４０ｇ／１
添加剤： ３−メルカプト１−プロパンスルホン酸ナトリウム＝１〜１０ｐｐｍ
ヒドロキシエチルセルロース＝1〜１００ｐｐｍ
低分子量膠（分子量３，０００）＝１〜５０ｐｐｍ
塩化物イオン濃度＝１０〜５０ｐｐｍ
温度： ５０〜６０℃Hereinafter, the present invention will be specifically described by Examples 1 to 9 and Comparative Examples 1 to 6.
[Copper foil production]
[Examples 1 to 9]
[Comparative Examples 1-6]
In Examples 1 to 9 and Comparative Examples 1 to 6, the current density was 50 to 100 A / dm 2 using a noble metal oxide-coated titanium electrode as the anode and a titanium rotating drum as the cathode under the following conditions. An electrolytic copper foil having a thickness of 10 μm was manufactured.
Copper: 70-130 g / 1
Sulfuric acid: 80-140 g / 1
Additive: 3-Mercapto1-sodium propanesulfonate = 1-10 ppm
Hydroxyethyl cellulose = 1-100ppm
Low molecular weight glue (molecular weight 3,000) = 1-50ppm
Chloride ion concentration = 10-50ppm
Temperature: 50-60 ° C

〔比較例７〜８〕
比較例７〜８は、実施例１〜９、および、比較例１〜６の低分子膠（分子量３，０００）の添加量を、５０ｐｐｍを超えて５００ｐｐｍ以下となる範囲に変更し、アノードには貴金属酸化物被覆チタン電極、カソードにはチタン製回転ドラムを用いて、電流密度＝５０〜１００Ａ／ｄｍ2で、厚さ１０μｍの電解銅箔を製造した。[Comparative Examples 7-8]
In Comparative Examples 7 to 8, the addition amount of the low molecular weight glue (molecular weight 3,000) of Examples 1 to 9 and Comparative Examples 1 to 6 was changed to a range of more than 50 ppm and 500 ppm or less. Was a noble metal oxide-coated titanium electrode, and a titanium rotating drum was used as the cathode to produce an electrolytic copper foil having a current density of 50 to 100 A / dm 2 and a thickness of 10 μm.

〔有機防錆皮膜形成〕
〔実施例１〜９〕
実施例１〜９は、電解製箔された銅箔をただちに濃度５０〜１０００ｐｐｍ未満のベンゾトリアゾール防錆溶液に浸漬し、株式会社日放電子製NVC-R1500を使用してプラズマ処理した市販のＳＵＳ３０４ロール（直径１２０ｍｍ、面長１０００ｍｍ、肉厚１５ｍｍ）を２本使用して両面の塗布を行い、有機皮膜量を一定量にコントロールし、銅箔表面に有機防錆皮膜を施した。なお、液温は３５〜５５℃、ｐＨは６．５〜８．０とした。[Organic rust prevention film formation]
[Examples 1 to 9]
In Examples 1 to 9, commercially available SUS304 obtained by immediately immersing an electrolytically formed copper foil in a benzotriazole rust preventive solution having a concentration of 50 to less than 1000 ppm and plasma-treating it using NVC-R1500 manufactured by Nikkiso Co., Ltd. Two rolls (diameter: 120 mm, surface length: 1000 mm, wall thickness: 15 mm) were applied on both sides, the amount of the organic film was controlled to a constant amount, and an organic rust preventive film was applied to the copper foil surface. The liquid temperature was 35 to 55 ° C., and the pH was 6.5 to 8.0.

〔比較例１〜２〕
比較例１〜２は、電解製箔された銅箔をただちに濃度５０〜１０００ｐｐｍ未満のベンゾトリアゾール防錆溶液に浸漬し、プラズマによる親水化処理を行っていない市販のＳＵＳ３０４ロール（直径１２０ｍｍ、面長１０００ｍｍ、肉厚１５ｍｍ）を２本使用して両面の塗布を行い、有機皮膜量を一定量にコントロールし、銅箔表面に有機防錆皮膜を施した。なお、液温は３５〜５５℃、ｐＨは６．５〜８．０とした。[Comparative Examples 1-2]
In Comparative Examples 1 and 2, a commercially available SUS304 roll (diameter 120 mm, surface length) in which the electrolytically formed copper foil was immediately immersed in a benzotriazole rust preventive solution having a concentration of 50 to less than 1000 ppm and was not subjected to a hydrophilic treatment by plasma. 1000 mm, thickness 15 mm) were used on both sides, the amount of the organic film was controlled to a fixed amount, and an organic rust preventive film was applied to the copper foil surface. The liquid temperature was 35 to 55 ° C., and the pH was 6.5 to 8.0.

〔比較例３〜４〕
比較例３〜４は、電解製箔された銅箔をただちに濃度１０〜５０ｐｐｍのベンゾトリアゾール防錆溶液に浸漬し、株式会社日放電子製NVC-R1500を使用してプラズマ処理した市販のＳＵＳ３０４ロール（直径１２０ｍｍ、面長１０００ｍｍ、肉厚１５ｍｍ）を２本使用して両面の塗布を行い、有機皮膜量を一定量にコントロールし、銅箔表面に有機防錆皮膜を施した。なお、液温は３５〜５５℃、ｐＨは６．５〜８．０とした。[Comparative Examples 3 to 4]
Comparative Examples 3 to 4 are commercially available SUS304 rolls obtained by immediately immersing an electrolytically formed copper foil in a benzotriazole rust preventive solution having a concentration of 10 to 50 ppm and plasma-treating using NVC-R1500 manufactured by Nikkiso Co., Ltd. Two surfaces (diameter 120 mm, surface length 1000 mm, wall thickness 15 mm) were used to apply both surfaces, the amount of the organic film was controlled to a constant amount, and an organic rust preventive film was applied to the copper foil surface. The liquid temperature was 35 to 55 ° C., and the pH was 6.5 to 8.0.

〔比較例５〜６〕
比較例５〜６は、電解製箔された銅箔をただちに濃度１０００〜５０００ｐｐｍのベンゾトリアゾール防錆溶液に浸漬し、株式会社日放電子製NVC-R1500を使用してプラズマ処理した市販のＳＵＳ３０４ロール（直径１２０ｍｍ、面長１０００ｍｍ、肉厚１５ｍｍ）を２本使用して両面の塗布を行い、有機皮膜量を一定量にコントロールし、銅箔表面に有機防錆皮膜を施した。なお、液温は３５〜５５℃、ｐＨは６．５〜８．０とした。[Comparative Examples 5-6]
Comparative Examples 5 to 6 are commercially available SUS304 rolls obtained by immediately immersing electrolytically produced copper foil in a benzotriazole rust preventive solution having a concentration of 1000 to 5000 ppm and plasma-treating using NVC-R1500 manufactured by Nikkiso Co., Ltd. Two surfaces (diameter 120 mm, surface length 1000 mm, wall thickness 15 mm) were used to apply both surfaces, the amount of the organic film was controlled to a constant amount, and an organic rust preventive film was applied to the copper foil surface. The liquid temperature was 35 to 55 ° C., and the pH was 6.5 to 8.0.

〔比較例７〜８〕
比較例７〜８は、電解製箔された銅箔をただちに濃度５０〜１０００ｐｐｍ未満のベンゾトリアゾール防錆溶液に浸漬し、株式会社日放電子製NVC-R1500を使用してプラズマ処理した市販のＳＵＳ３０４ロール（直径１２０ｍｍ、面長１０００ｍｍ、肉厚１５ｍｍ）を２本使用して両面の塗布を行い、有機皮膜量を一定量にコントロールし、銅箔表面に有機防錆皮膜を施した。なお、液温は３５〜５５℃、ｐＨは６．５〜８．０とした。[Comparative Examples 7-8]
In Comparative Examples 7 to 8, commercially available SUS304 obtained by immediately immersing an electrolytically formed copper foil in a benzotriazole rust-preventing solution having a concentration of 50 to less than 1000 ppm and plasma-treating it using NVC-R1500 manufactured by Nikkiso Co., Ltd. Two rolls (diameter: 120 mm, surface length: 1000 mm, wall thickness: 15 mm) were applied on both sides, the amount of the organic film was controlled to a constant amount, and an organic rust preventive film was applied to the copper foil surface. The liquid temperature was 35 to 55 ° C., and the pH was 6.5 to 8.0.

〔活物質層の形成と密着性の評価〕
上述した、各実施例、各比較例で作成した表面処理銅箔の表面に下記炭素材料からなる活物質スラリーペーストを用い、銅箔と活物質の密着性を下記により評価した。
その結果を表１（実施例）および表２（比較例）に示す。
炭素材料としては、塊状人造黒鉛を用い、該塊状人造黒鉛をＮＭＰに８％ＰＶＤＦ（ポリフッ化ビニリデン）粉を溶かした溶液と混合してペースト状とし、このペーストを銅箔表面に約５０μｍの厚さに塗布して、８０℃で３時間乾燥後圧延によるプレスを行い、さらに真空乾燥した。
この活物質塗布面に両面テープを貼り付け、支持板にも両面テープを貼り付け、両面テープ同士を張り合わせた。そして、ＪＩＳＣ６４７１に準じる方法で引き剥がし角度９０度にて剥離強度を測定した。
表１および表２において、接着強度が４０００ｇ／ｃｍを超えるものを◎、３０００ｇ／ｃｍ以上４０００ｇ／ｃｍ未満となるものを○、１０００ｇ／ｃｍ以上３０００ｇ／ｃｍ未満となるものを△、１０００ｇ／ｃｍに未満のものを×とした。[Formation of active material layer and evaluation of adhesion]
The active material slurry paste which consists of the following carbon material was used for the surface of the surface treatment copper foil created by each Example and each comparative example mentioned above, and the adhesiveness of copper foil and an active material was evaluated by the following.
The results are shown in Table 1 (Examples) and Table 2 (Comparative Examples).
As the carbon material, massive artificial graphite is used, and the massive artificial graphite is mixed with a solution obtained by dissolving 8% PVDF (polyvinylidene fluoride) powder in NMP to form a paste. Then, it was dried at 80 ° C. for 3 hours, pressed by rolling, and further vacuum dried.
Double-sided tape was affixed to this active material application surface, double-sided tape was also affixed to the support plate, and the double-sided tapes were bonded together. And the peeling strength was measured by the method according to JISC6471 at the peeling angle of 90 degree | times.
In Tables 1 and 2, those having an adhesive strength exceeding 4000 g / cm are: ◎, those having 3000 g / cm or more and less than 4000 g / cm, Δ, those having 1000 g / cm or more and less than 3000 g / cm, Δ, 1000 g / cm Those less than 2 were marked with x.

〔窒素及び炭素の検出深さ範囲の測定〕
窒素及び炭素の検出深さ範囲を、アルバック・ファイ株式会社製ＸＰＳ測定装置５６００ＭＣを使用し下記条件で測定した。
到達真空度１×１０-10Ｔｏｒｒ（Ａｒガス導入時１×１０-8Ｔｏｒｒ）、
Ｘ線：Ｘ線種単色化Ａｌ−ｋα線、
出力３００Ｗ、
検出面積８００μｍφ、
イオン線：イオン種Ａｒ+、
加速電圧３ｋＶ、
掃引面積３×３ｍｍ2、
試料入射角４５°（試料と検出器とのなす角）、
スパッタリングレート２．３ｎｍ／分（ＳｉＯ2換算）[Measurement of detection depth range of nitrogen and carbon]
The detection depth range of nitrogen and carbon was measured under the following conditions using an XPS measuring device 5600MC manufactured by ULVAC-PHI CORPORATION.
Ultimate vacuum 1 × 10 −10 Torr (1 × 10 −8 Torr when Ar gas is introduced),
X-ray: X-ray type monochromatic Al-kα ray,
300W output,
Detection area 800μmφ,
Ion beam: Ion species Ar +,
Acceleration voltage 3kV,
Sweep area 3 × 3mm 2 ,
Sample incident angle 45 ° (angle formed between sample and detector),
Sputtering rate 2.3 nm / min (SiO 2 conversion)

〔不純物量の測定〕
銅箔中に含まれる不純物元素について、以下の測定手法、及び測定機器を用いて測定した。
Ｃ、Ｓ：燃焼−赤外線吸収法、ＣＳ８４４（ＬＥＣＯ社製）、
Ｏ、Ｎ：不活性ガス融解−熱伝導度法、ＯＮＨ８３６（ＬＥＣＯ社製）、
Ｃｌ：熱加水分解−イオンクロマトグラフ法、ＤＸ−５００（日本ダイオネクス製）(Measurement of impurities)
About the impurity element contained in copper foil, it measured using the following measuring methods and measuring instruments.
C, S: Combustion-infrared absorption method, CS844 (manufactured by LECO),
O, N: Inert gas melting-thermal conductivity method, ONH836 (manufactured by LECO),
Cl: thermal hydrolysis-ion chromatography, DX-500 (manufactured by Nippon Dionex)

〔耐酸化性の評価〕
以下の手法により、銅箔の耐酸化性を評価した。
(1) 塩ビパイプ（内径３２ｍｍ、外径３８ｍｍ、長さ１０ｃｍ）に、銅箔（７０ｍｍ×３００ｍｍ）をまきつけて、試料を作成した。
(2) (1)の処理で作成した試料を恒温恒湿機（６０℃、９０ＲＨ％）にセットし、５日間（１２０時間）保持した。
(3) 試料を(2)の処理を行う試験機から取り出し、銅箔表面の、銅箔同士が重なり合っていた部分の色調を確認した。
(4) 評価方法、試験前と比較して色調に変化がなければ○、青もしくは紫色の著しい変色となった場合には×とした。[Evaluation of oxidation resistance]
The oxidation resistance of the copper foil was evaluated by the following method.
(1) A copper foil (70 mm × 300 mm) was wound around a PVC pipe (inner diameter: 32 mm, outer diameter: 38 mm, length: 10 cm) to prepare a sample.
(2) The sample prepared by the treatment in (1) was set in a thermo-hygrostat (60 ° C., 90 RH%) and held for 5 days (120 hours).
(3) The sample was taken out from the testing machine that performs the treatment of (2), and the color tone of the portion of the copper foil surface where the copper foils overlapped was confirmed.
(4) If the color tone does not change compared to the evaluation method and before the test, it was marked as x when the color changed markedly ○, blue or purple.

Figure 2014178327
Figure 2014178327

Figure 2014178327
Figure 2014178327

実施例１〜５は、不純物量の合計が１０ｐｐｍ以下に抑えられ、窒素及び炭素の検出深さの範囲が０．２ｎｍ以上２．０ｎｍ未満の範囲に抑えられているため、活物質の密着性は良好なものとなっている。
実施例６〜９は、不純物量の合計が１０ｐｐｍを超えるものの２０ｐｐｍ以下に抑えられ、窒素及び炭素の検出深さの範囲が０．２ｎｍ以上２．０ｎｍ未満の範囲に抑えられているため、活物質の密着性はほぼ良好なものとなっている。In Examples 1 to 5, the total amount of impurities is suppressed to 10 ppm or less, and the range of detection depth of nitrogen and carbon is suppressed to a range of 0.2 nm or more and less than 2.0 nm. Is good.
In Examples 6 to 9, although the total amount of impurities exceeds 10 ppm, it is suppressed to 20 ppm or less, and the range of the detection depth of nitrogen and carbon is suppressed to a range of 0.2 nm to less than 2.0 nm. The adhesion of the substance is almost good.

比較例１〜２は、プラズマによる親水化を行ったロールを使用しているものの、０．１ｎｍと防錆成分の皮膜厚さが不足している。このため、活物質塗布後の乾燥工程における銅箔表面の酸化膜が大きく成長するため、活物質の密着性はやや不良なものとなっている。
比較例３〜４は、防錆成分の皮膜厚さが２．０ｎｍを超えた過剰なものとなっており、プラズマによる親水化を行ったロールを使用しても皮膜の均一性を確保できず、活物質ペーストの均一な塗布ができない。このため、活物質の密着性はやや不良なものとなっている。
比較例５〜６は、箔中の不純物量が５５ｐｐｍ以上と過剰となっているため、銅箔表面の防錆成分の皮膜厚さを最適化し、プラズマによる親水化処理を行ったロールにより処理を行っても防錆皮膜の均一性が確保できず、活物質ペーストの均一な塗布ができない。このため、活物質の密着性はやや不良なものとなっている。Although Comparative Examples 1-2 uses the roll which hydrophilized by plasma, 0.1 nm and the film thickness of an antirust component are insufficient. For this reason, since the oxide film on the copper foil surface in the drying step after the application of the active material grows greatly, the adhesion of the active material is somewhat poor.
In Comparative Examples 3 to 4, the film thickness of the anticorrosive component is excessive, exceeding 2.0 nm, and the uniformity of the film cannot be ensured even when using a roll hydrophilized by plasma. The active material paste cannot be uniformly applied. For this reason, the adhesion of the active material is somewhat poor.
In Comparative Examples 5 to 6, since the amount of impurities in the foil is excessively 55 ppm or more, the film thickness of the anticorrosive component on the surface of the copper foil is optimized, and the treatment is performed with a roll subjected to a hydrophilic treatment by plasma. Even if it is performed, the uniformity of the rust preventive film cannot be secured, and the active material paste cannot be uniformly applied. For this reason, the adhesion of the active material is somewhat poor.

以上述べたように、本発明の銅箔の表面に表面処理皮膜を有する表面処理銅箔は、銅箔中に含まれる不純物である炭素、硫黄、酸素、窒素、塩素の含有量の合計が２０ｐｐｍ以下であり、かつ、ＸＰＳ（Ｘ線光電子分光分析）により窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上２．０ｎｍ未満であるとすることにより、負極活物質との接着性が向上する。
また、銅箔中に含まれる不純物である炭素、硫黄、酸素、窒素、塩素の含有量の合計が１０ｐｐｍ以下であり、かつ、ＸＰＳ（Ｘ線光電子分光分析）により窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上２．０ｎｍ未満であるとすることにより、負極活物質との接着性が向上する。
また、銅箔中に含まれる炭素、硫黄、酸素、窒素、塩素の含有量の合計が２０ｐｐｍ以下であり、かつ、ＸＰＳ（Ｘ線光電子分光分析）により窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上１．０ｎｍ以下とすることにより、負極活物質との接着性が向上する。
また、銅箔中に含まれる不純物である炭素、硫黄、酸素、窒素、塩素の含有量の合計が１０ｐｐｍ以下であり、かつ、ＸＰＳ（Ｘ線光電子分光分析）により窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上１．０ｎｍ以下であるとすることにより、負極活物質との接着性が向上する。As described above, the surface-treated copper foil having a surface-treated film on the surface of the copper foil of the present invention has a total content of carbon, sulfur, oxygen, nitrogen, and chlorine, which are impurities contained in the copper foil, of 20 ppm. And the depth range detected by XPS (X-ray photoelectron spectroscopy) to be greater than the background level of nitrogen and carbon is 0.2 nm or more and less than 2.0 nm. Adhesiveness is improved.
Also, the total content of carbon, sulfur, oxygen, nitrogen and chlorine, which are impurities contained in the copper foil, is 10 ppm or less, and from the background level of nitrogen and carbon by XPS (X-ray photoelectron spectroscopy) In addition, when the depth range in which the depth is greatly detected is 0.2 nm or more and less than 2.0 nm, the adhesion to the negative electrode active material is improved.
Also, the total content of carbon, sulfur, oxygen, nitrogen, and chlorine contained in the copper foil is 20 ppm or less, and it is detected by XPS (X-ray photoelectron spectroscopy) to be larger than the background level of nitrogen and carbon. By setting the depth range to be 0.2 nm or more and 1.0 nm or less, the adhesion with the negative electrode active material is improved.
Also, the total content of carbon, sulfur, oxygen, nitrogen and chlorine, which are impurities contained in the copper foil, is 10 ppm or less, and from the background level of nitrogen and carbon by XPS (X-ray photoelectron spectroscopy) If the depth range in which the depth is detected is 0.2 nm or more and 1.0 nm or less, the adhesion with the negative electrode active material is improved.

産業上の利用分野Industrial application fields

本発明の本発明の銅箔は、たとえば、リチウムイオン二次電池の集電体として好適に使用することができる。   The copper foil of the present invention of the present invention can be suitably used, for example, as a current collector for a lithium ion secondary battery.

Claims (6)

銅箔の表面に表面処理皮膜を有する表面処理銅箔であって、
当該銅箔中に含まれる炭素、硫黄、酸素、窒素、塩素の含有量の合計が２０ｐｐｍ以下であり、かつ、ＸＰＳ（Ｘ線光電子分光分析）により窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上２．０ｎｍ未満である、
リチウムイオン二次電池負極集電体用表面処理銅箔。A surface-treated copper foil having a surface-treated film on the surface of the copper foil,
The total content of carbon, sulfur, oxygen, nitrogen, and chlorine contained in the copper foil is 20 ppm or less, and is detected to be larger than the background level of nitrogen and carbon by XPS (X-ray photoelectron spectroscopy). The depth range is 0.2 nm or more and less than 2.0 nm,
A surface-treated copper foil for a negative electrode current collector of a lithium ion secondary battery. 当該銅箔中に含まれる炭素、硫黄、酸素、窒素、塩素の含有量の合計が１０ｐｐｍ以下である、
請求項１に記載のリチウムイオン二次電池負極集電体用表面処理銅箔。The total content of carbon, sulfur, oxygen, nitrogen, and chlorine contained in the copper foil is 10 ppm or less.
The surface-treated copper foil for lithium ion secondary battery negative electrode collectors of Claim 1. 前記ＸＰＳ（Ｘ線光電子分光分析）により窒素および炭素のバックグラウンドレベルよりも大きく検出される深さ範囲が０．２ｎｍ以上１．０ｎｍ以下である、
請求項１に記載のリチウムイオン二次電池負極集電体用表面処理銅箔。The depth range detected to be larger than the background level of nitrogen and carbon by XPS (X-ray photoelectron spectroscopy) is 0.2 nm or more and 1.0 nm or less.
The surface-treated copper foil for lithium ion secondary battery negative electrode collectors of Claim 1. 前記銅箔中に含まれる炭素・硫黄・酸素・窒素・塩素の含有量の合計が１０ｐｐｍ以下である、
請求項３に記載のリチウムイオン二次電池負極集電体用表面処理銅箔。The total content of carbon, sulfur, oxygen, nitrogen and chlorine contained in the copper foil is 10 ppm or less,
The surface-treated copper foil for lithium ion secondary battery negative electrode collectors of Claim 3. 前記銅箔表面に、親水化法による有機防錆皮膜が均一な膜厚で形成されている、
請求項１〜４のいずれかに記載のリチウムイオン二次電池負極集電体用銅箔。On the copper foil surface, an organic rust preventive film by a hydrophilization method is formed with a uniform film thickness,
The copper foil for lithium ion secondary battery negative electrode collectors in any one of Claims 1-4. 前記銅箔は、電解銅箔、電解銅合金箔及び圧延銅箔及び圧延銅合金箔のいずれかである、
請求項１〜５のいずれかに記載のリチウムイオン二次電池負極集電体用銅箔。The copper foil is one of an electrolytic copper foil, an electrolytic copper alloy foil, a rolled copper foil and a rolled copper alloy foil.
The copper foil for lithium ion secondary battery negative electrode collectors in any one of Claims 1-5.
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