TW201829849A - Surface-treated copper foil, and current collector, electrode, and battery cell using the surface-treated copper foil - Google Patents

Abstract

The surface-treated copper foil for a battery cell according to one or more embodiments of the present application contains a copper foil and a surface treatment layer on at least one surface of the copper foil, wherein the surface treatment layer contains a primary particle layer and a secondary particle layer, and the surface of the surface treatment layer has a ten-point average roughness Rz of 1.8 [mu]m or more measured with a laser microscope with a wavelength of 405 nm according to JIS B0601 1994.

Description

表面處理銅箔以及使用其之集電體、電極及電池  Surface treated copper foil and current collector, electrode and battery using same  

本發明係關於一種表面處理銅箔以及使用其之集電體、電極及電池。 The present invention relates to a surface treated copper foil and a current collector, an electrode and a battery using the same.

作為電池、尤其是二次電池的負極用或電極用集電體，使用壓延銅箔和電解銅箔。對於任一銅箔，均要求正極或負極活性物質與作為集電體的銅箔的高密接性。為了改善密接性，有進行對銅箔表面實施形成凹凸的表面處理的例子。例如，如專利文獻1所公開般，通過用砂紙對銅箔表面進行研磨而形成凹凸，從而實現密接性的改善。 As a battery, in particular, a negative electrode for a secondary battery or a current collector for an electrode, a rolled copper foil and an electrolytic copper foil are used. For any copper foil, high adhesion between the positive electrode or the negative electrode active material and the copper foil as a current collector is required. In order to improve the adhesion, there is an example in which a surface treatment for forming irregularities on the surface of the copper foil is performed. For example, as disclosed in Patent Document 1, the surface of the copper foil is polished with sandpaper to form irregularities, thereby improving the adhesion.

[背景技術文獻] [Background literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利第3733067號公報 [Patent Document 1] Japanese Patent No. 3733067

然而，存在如下問題：即便如專利文獻1所記載般單純地通過利用砂紙等研磨紙對銅箔進行研磨而形成凹凸，也無法獲得集電體銅箔與活性物質的充分的密接性。 However, there is a problem in that, as described in Patent Document 1, the copper foil is polished by polishing paper such as sandpaper to form irregularities, and sufficient adhesion between the current collector copper foil and the active material cannot be obtained.

另外，在銅箔設置由粗化鍍覆所獲得的粗化處理層而形成凹凸的情況下，有大量地產生粗化粒子層的粗化粒子的脫落的問題。 In addition, when the roughened layer obtained by roughening plating is provided in the copper foil to form irregularities, there is a problem that a large amount of roughened particles of the roughened particle layer fall off.

本發明的課題在於提供一種電池用表面處理銅箔，其粗化粒子的脫落少，能夠獲得與活性物質的良好的密接性。 An object of the present invention is to provide a surface-treated copper foil for a battery which has less detachment of coarsened particles and which can provide good adhesion to an active material.

本發明人等對以往技術中未能獲得充分的密接性的理由努力進行研究，結果發現如下問題：使用硫酸銅鍍浴通過粗化處理而在銅箔表面形成的粗化粒子因肥大化的粗化粒子的堆積而不均勻。即，存在如下問題：粗化粒子以銅粉的形式從粗化粒子堆積的部分脫落，由此無法獲得集電體銅箔與活性物質的充分的密接性。因此，本發明人等發現，通過控制在銅箔的表面側形成一次粒子層及二次粒子層所獲得的表面處理層的十點平均粗糙度Rz，而與活性物質的密接性變得良好。而且，本發明是基於所述見解而完成的。 The inventors of the present invention have conducted research on the reasons for failing to obtain sufficient adhesion in the prior art, and as a result, have found that coarsened particles formed on the surface of the copper foil by roughening treatment using a copper sulfate plating bath are coarsened by coarsening. The accumulation of particles is not uniform. That is, there is a problem in that the roughened particles are detached from the portion where the roughened particles are deposited in the form of copper powder, whereby sufficient adhesion between the current collector copper foil and the active material cannot be obtained. Therefore, the present inventors have found that the ten-point average roughness Rz of the surface-treated layer obtained by forming the primary particle layer and the secondary particle layer on the surface side of the copper foil is good, and the adhesion to the active material is good. Moreover, the present invention has been completed based on the above findings.

即，本發明是一種電池用表面處理銅箔，其具有銅箔及位於所述銅箔的至少一表面側的表面處理層，且所述表面處理層從所述銅箔的表面側依序具有一次粒子層、二次粒子層，且依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對所述電池用表面處理銅箔的表面處理層表面進行測量時的十點平均粗糙度Rz為1.8μm以上。 That is, the present invention is a surface-treated copper foil for a battery having a copper foil and a surface treatment layer on at least one surface side of the copper foil, and the surface treatment layer has a sequence from the surface side of the copper foil The primary particle layer and the secondary particle layer have a ten-point average roughness Rz of 1.8 μm or more when the surface of the surface-treated layer of the surface-treated copper foil for a battery is measured using a laser microscope having a wavelength of 405 nm according to JIS B0601 1994. .

另外，在本發明的一實施形態中，依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對所述電池用表面處理銅箔的表面處理層表面進行測量時的算術平均粗糙度Ra為0.26μm以上。 Further, in an embodiment of the present invention, the arithmetic mean roughness Ra when the surface of the surface-treated layer of the surface-treated copper foil for a battery is measured using a laser microscope having a wavelength of 405 nm is set to be more than 0.26 μm in accordance with JIS B0601 1994. .

另外，在本發明的一實施形態中，所述一次粒子層含有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。 Furthermore, in the embodiment of the present invention, the primary particle layer contains one or more selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. .

另外，在本發明的一實施形態中，所述二次粒子層含有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。 Further, in an embodiment of the present invention, the secondary particle layer contains one selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. the above.

另外，在本發明的一實施形態中，所述表面處理層含有合計100μg/dm²以上的選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。 Furthermore, in one embodiment of the present invention, the surface treatment layer contains a total of 100 μg/dm ² or more selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. One or more of the group consisting of.

另外，在本發明的一實施形態中，所述表面處理層含有合計10000μg/dm²以下的選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。 Further, in one embodiment of the present invention, the surface treatment layer contains a total of 10000 μg/dm ² or less selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. One or more of the group consisting of.

另外，在本發明的一實施形態中，所述表面處理層含有Ni，且Ni的附著量為100μg/dm²以上。 Further, in an embodiment of the invention, the surface treatment layer contains Ni, and the adhesion amount of Ni is 100 μg/dm ² or more.

另外，在本發明的一實施形態中，所述表面處理層含有Ni，且Ni的附著量為4500μg/dm²以下。 Further, in an embodiment of the invention, the surface treatment layer contains Ni, and the adhesion amount of Ni is 4,500 μg/dm ² or less.

另外，在本發明的一實施形態中，所述表面處理層含有Co，且Co的附著量為100μg/dm²以上。 Further, in an embodiment of the invention, the surface treatment layer contains Co, and the adhesion amount of Co is 100 μg/dm ² or more.

另外，在本發明的一實施形態中，所述表面處理層含有Co，且Co的附著量為6000μg/dm²以下。 Further, in an embodiment of the invention, the surface treatment layer contains Co, and the adhesion amount of Co is 6000 μg/dm ² or less.

另外，在本發明的一實施形態中，所述一次粒子層由Cu構成。 Further, in an embodiment of the invention, the primary particle layer is made of Cu.

另外，在本發明的一實施形態中，所述二次粒子層由Cu、Co、Ni構成。 Further, in an embodiment of the invention, the secondary particle layer is made of Cu, Co, or Ni.

另外，在本發明的一實施形態中，所述銅箔含有合計5質量ppm以上且0.3質量%以下的選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及Mg所組成的群中的一種以上。 Furthermore, in one embodiment of the present invention, the copper foil contains a total of 5 mass ppm or more and 0.3 mass% or less selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, and Mn. One or more of the group consisting of Mo, Co, Ni, Si, Zr, B, and Mg.

另外，在本發明的一實施形態中，所述銅箔含有合計5質量ppm以上且300質量ppm以下的選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及Mg所組成的群中的一種以上。 Furthermore, in one embodiment of the present invention, the copper foil contains a total of 5 mass ppm or more and 300 mass ppm or less selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, and Mn. One or more of the group consisting of Mo, Co, Ni, Si, Zr, B, and Mg.

另外，在本發明的一實施形態中，所述銅箔含有合計301質量 ppm以上且0.3質量%以下的選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及Mg所組成的群中的一種以上。 Furthermore, in one embodiment of the present invention, the copper foil contains 301 mass ppm or more and 0.3 mass% or less in total selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, and Mn. One or more of the group consisting of Mo, Co, Ni, Si, Zr, B, and Mg.

另外，在本發明的一實施形態中，所述表面處理層在所述二次粒子層上進而具有選自由耐熱層、防銹層、鉻酸鹽處理層、矽烷偶合處理層、鍍覆層、樹脂層所組成的群中的1種以上的層。 Further, in an embodiment of the present invention, the surface treatment layer further has a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, a decane coupling treatment layer, a plating layer, and the plating layer on the secondary particle layer. One or more layers in the group consisting of the resin layers.

另外，在本發明的一實施形態中，本發明的電池用表面處理銅箔為二次電池用。 Moreover, in one embodiment of the present invention, the surface-treated copper foil for a battery of the present invention is used for a secondary battery.

另外，在本發明的一實施形態中，本發明的電池用表面處理銅箔為二次電池集電體用。 Further, in an embodiment of the present invention, the surface-treated copper foil for a battery of the present invention is used for a secondary battery current collector.

另外，本發明是一種集電體，其具有所述電池用表面處理銅箔。 Further, the present invention is a current collector having the surface-treated copper foil for a battery.

另外，本發明是一種電極，其具有所述電池用表面處理銅箔。 Further, the present invention is an electrode having the surface-treated copper foil for the battery.

另外，本發明是一種電池，其具有所述電池用表面處理銅箔或集電體或電極。 Further, the present invention is a battery comprising the surface-treated copper foil for a battery or a current collector or an electrode.

根據本發明，能夠獲得粗化粒子的脫落少而與活性物質的密接性良好的電池用表面處理銅箔。另外，根據本發明的一部分實施態樣，能夠獲得進而具備耐熱特性優異的表面處理層的電池用表面處理銅箔。 According to the present invention, it is possible to obtain a surface-treated copper foil for a battery which has less peeling of the roughened particles and has good adhesion to the active material. Further, according to a part of the embodiment of the present invention, it is possible to obtain a surface-treated copper foil for a battery which further has a surface treatment layer excellent in heat resistance.

圖1是表示對銅箔的表面進行以往的粗化處理時的粗化粒子的情況的概念圖。 FIG. 1 is a conceptual diagram showing a state in which roughened particles are subjected to a conventional roughening treatment on the surface of a copper foil.

圖2是表示本發明的具有表面處理層的電池用表面處理銅箔的表面處理層 的情況的概念圖。 Fig. 2 is a conceptual view showing a state of a surface treatment layer of a surface-treated copper foil for a battery having a surface treatment layer of the present invention.

<電池用表面處理銅箔> <Battery surface treated copper foil>

本發明的電池用表面處理銅箔(包含銅合金箔)例如可作為電池或二次電池的集電體而在其上形成活性物質薄膜來製作電極，最終製造以該電極作為電極(可為正極或負極中的任一個)的電池或二次電池。在集電體上形成活性物質薄膜的方法並無特別限定，例如可列舉CVD法、濺鍍法、蒸鍍法、溶射法、將含有活性物質的液體塗布於集電體上後進行乾燥的方法或鍍覆法等。這些薄膜形成方法中，特佳為使用CVD法、濺鍍法、及蒸鍍法。另外，也可在集電體上形成中間層，在該中間層上形成活性物質薄膜。本發明的電池用表面處理銅箔能夠用於公知電極、公知集電體、公知電池。作為公知電池，例如可列舉鋰離子二次電池、全固體二次電池、空氣電池(鋰-空氣電池、鋅-空氣電池等)、鈉離子電池、鎂離子電池、多價離子電池、正極使用硫系物質的二次電池、正極使用顯示氧化還原活性的有機物的二次電池、鎳/鎘電池、錳電池(乾電池)、鹼性電池(乾電池)、鋰電池(乾電池)等。作為公知電極、公知集電體，可列舉用於所述公知電池的電極、集電體。 The surface-treated copper foil for a battery of the present invention (including a copper alloy foil) can be used as a current collector of a battery or a secondary battery to form an active material film thereon to form an electrode, and the electrode can be used as an electrode (which can be a positive electrode). A battery or a secondary battery of either one of the negative electrodes. The method of forming the active material film on the current collector is not particularly limited, and examples thereof include a CVD method, a sputtering method, a vapor deposition method, a spray method, and a method in which a liquid containing an active material is applied onto a current collector and then dried. Or plating method, etc. Among these film forming methods, a CVD method, a sputtering method, and a vapor deposition method are particularly preferable. Further, an intermediate layer may be formed on the current collector, and an active material film is formed on the intermediate layer. The surface-treated copper foil for a battery of the present invention can be used for a known electrode, a known current collector, or a known battery. Examples of the known battery include a lithium ion secondary battery, an all solid secondary battery, an air battery (a lithium-air battery, a zinc-air battery, etc.), a sodium ion battery, a magnesium ion battery, a multivalent ion battery, and a sulfur for a positive electrode. A secondary battery of a substance, a secondary battery of an organic substance exhibiting redox activity, a nickel/cadmium battery, a manganese battery (dry battery), an alkaline battery (dry battery), a lithium battery (dry battery), or the like. Examples of the known electrode and the known current collector include an electrode and a current collector used in the known battery.

<銅箔> <copper foil>

本發明可使用的銅箔的形態並無特別限制，可使用公知銅箔。本發明中使用的銅箔典型可為通過乾式鍍覆或濕式鍍覆形成的銅箔、電解銅箔或壓延銅箔的任一者。一般而言，電解銅箔是從硫酸銅鍍浴中將銅電解析出至鈦或不銹鋼的滾筒上而製造。另外，壓延銅箔是反復進行利用壓延輥的塑性加工和熱處理來製造。對於要求撓曲性的用途，多數情況下應用壓延銅箔。在使用所述銅箔、例如壓延銅箔的情況下，也可使用在壓延後等製造銅箔後進行退火處理 (annealing treatment)的銅箔。就提高耐彎曲性等而言，較佳為進行退火處理的壓延銅箔。 The form of the copper foil which can be used in the present invention is not particularly limited, and a known copper foil can be used. The copper foil used in the present invention may typically be any of copper foil, electrolytic copper foil or rolled copper foil formed by dry plating or wet plating. In general, an electrolytic copper foil is produced by extracting copper from a copper sulfate plating bath onto a drum of titanium or stainless steel. Further, the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. For applications requiring flexibility, calendered copper foil is used in most cases. In the case of using the copper foil, for example, a rolled copper foil, a copper foil which is subjected to an annealing treatment after the copper foil is produced after rolling or the like may be used. In order to improve bending resistance and the like, a rolled copper foil subjected to annealing treatment is preferred.

作為銅箔材料，除韌銅(JIS H3100合金編號C1100)或無氧銅(JIS H3100合金編號C1020或JIS H3510合金編號C1011)或磷去氧銅(JIS H3100合金編號C1201、C1220或C1221)或電解銅之類的高純度銅以外，也可使用例如加入Sn的銅、加入Ag的銅、在所述高純度的銅中添加選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及/或Mg等所組成的群中的一種以上的銅合金、添加Ni及Si等的科森系銅合金之類的銅合金。另外，也可使用具有公知組成的銅箔及銅合金箔。此外，本說明書中，單獨使用用語「銅箔」時，也包含銅合金箔。另外，作為銅箔材料，也可使用在所述高純度銅中添加合計5質量ppm以上、較佳為10質量ppm以上、較佳為15質量ppm以上、較佳為20質量ppm以上、較佳為25質量ppm以上、較佳為30質量ppm以上、較佳為35質量ppm以上、較佳為40質量ppm以上、較佳為45質量ppm以上、較佳為50質量ppm以上、較佳為301質量ppm以上、較佳為310質量ppm以上、較佳為350質量ppm以上、較佳為380質量ppm以上、較佳為400質量ppm以上、較佳為500質量ppm以上的選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及Mg所組成的群中的一種以上的銅合金。另外，作為銅箔材料，也可使用在所述高純度銅中添加合計50質量%以下、較佳為40質量%以下、較佳為30質量%以下、較佳為20質量%以下、較佳為10質量%以下、較佳為5質量%以下、較佳為1質量%以下、較佳為0.8質量%以下、較佳為0.6質量%以下、較佳為0.5質量%以下、較佳為0.3質量%以下、較佳為0.28質量%以下、較佳為0.25質量%以下、較佳為0.23質量%以下、較佳為0.20質量%以下、較佳為0.17質量%以下、較佳為0.15質量%以下、較佳為300質量ppm以下的選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、 Zr、B及Mg所組成的群中的一種以上的銅合金。在添加到所述高純度銅中的選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及Mg所組成的群中的一種以上的元素的合計濃度高的情況下(例如301質量ppm以上)，銅箔的強度進一步變高，因此有效。另外，在選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及Mg所組成的群中的一種以上的元素的合計濃度低的情況下(例如300質量ppm以下)，彎曲性優異，因此有效。 As the copper foil material, in addition to tough pitch copper (JIS H3100 alloy number C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011) or phosphorus deoxidized copper (JIS H3100 alloy number C1201, C1220 or C1221) or electrolysis In addition to high-purity copper such as copper, for example, copper to which Sn is added, copper to which Ag is added, and copper to be added to the high-purity copper may be selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, One or more copper alloys of a group consisting of Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B, and/or Mg, and a copper alloy such as a Corson-based copper alloy such as Ni or Si. . Further, a copper foil and a copper alloy foil having a known composition can also be used. In addition, in the present specification, when the term "copper foil" is used alone, a copper alloy foil is also included. Further, as the copper foil material, a total of 5 ppm by mass or more, preferably 10 ppm by mass or more, preferably 15 ppm by mass or more, preferably 20 ppm by mass or more, preferably 20 parts by mass or more, preferably, is added to the high-purity copper. It is 25 mass ppm or more, preferably 30 mass ppm or more, preferably 35 mass ppm or more, preferably 40 mass ppm or more, preferably 45 mass ppm or more, preferably 50 mass ppm or more, and more preferably 301. The mass is ppm or more, preferably 310 mass ppm or more, preferably 350 mass ppm or more, preferably 380 mass ppm or more, preferably 400 mass ppm or more, and more preferably 500 mass ppm or more, selected from In, Au, and One or more copper alloys of a group consisting of Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B, and Mg. In addition, as the copper foil material, a total of 50% by mass or less, preferably 40% by mass or less, preferably 30% by mass or less, preferably 20% by mass or less, preferably, is preferably added to the high-purity copper. It is 10% by mass or less, preferably 5% by mass or less, preferably 1% by mass or less, preferably 0.8% by mass or less, preferably 0.6% by mass or less, preferably 0.5% by mass or less, preferably 0.3% by mass. The mass% or less, preferably 0.28% by mass or less, preferably 0.25 mass% or less, preferably 0.23% by mass or less, preferably 0.20% by mass or less, preferably 0.17% by mass or less, preferably 0.15% by mass. Hereinafter, it is preferably 300 mass ppm or less selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B, and Mg. More than one copper alloy in the group. The addition to the high-purity copper is selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B, and Mg. When the total concentration of one or more elements in the group is high (for example, 301 mass ppm or more), the strength of the copper foil is further increased, which is effective. Further, one or more elements selected from the group consisting of In, Au, Pd, Ag, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B, and Mg When the total concentration is low (for example, 300 ppm by mass or less), the flexibility is excellent, and therefore it is effective.

<表面處理層> <surface treatment layer>

表面處理層從銅箔側依序具有一次粒子層及二次粒子層。通過表面處理層從銅箔側依序具有一次粒子層和二次粒子層，而減少因粗化粒子的脫落所引起的粉體脫落。另外，通過表面處理層從銅箔側依序具有一次粒子層和二次粒子層，而具有銅箔與活性物質的密接性變得良好的效果。推斷其原因在於，通過設置一次粒子層和二次粒子層而粗化粒子變得不易折斷。另外，通過表面處理層從銅箔側依序具有一次粒子層和二次粒子層，銅箔的耐熱性提升。一次粒子層及二次粒子層可利用電鍍層來形成。該二次粒子的特徵為在所述一次粒子上生成的1個或多個粒子。或者，二次粒子層是在所述一次粒子上生成的正常鍍覆層。二次粒子也可具有樹枝狀的形狀。即，本說明書中，在使用用語「二次粒子層」的情況下，也包含覆蓋鍍覆等正常鍍覆層。另外，二次粒子層可為具有一層以上的由粗化粒子所形成的層的層，可為具有一層以上的正常鍍覆層的層，也可為分別具有一層以上的由粗化粒子所形成的層和正常鍍覆層的層。此外，表面處理層也可具有一次粒子層或二次粒子層以外的一層或多層其他層。此外，所謂正常鍍覆是指在極限電流密度以下的電流密度的條件下進行的鍍覆。 The surface treatment layer sequentially has a primary particle layer and a secondary particle layer from the side of the copper foil. The surface treatment layer sequentially has a primary particle layer and a secondary particle layer from the side of the copper foil, thereby reducing powder shedding due to falling off of the coarsened particles. In addition, the surface treatment layer has a primary particle layer and a secondary particle layer in this order from the copper foil side, and has an effect of improving the adhesion between the copper foil and the active material. It is presumed that the reason is that roughening of the particles by setting the primary particle layer and the secondary particle layer becomes difficult to break. Further, the surface treatment layer sequentially has a primary particle layer and a secondary particle layer from the side of the copper foil, and the heat resistance of the copper foil is improved. The primary particle layer and the secondary particle layer can be formed using a plating layer. The secondary particle is characterized by one or a plurality of particles generated on the primary particle. Alternatively, the secondary particle layer is a normal plating layer formed on the primary particles. The secondary particles may also have a dendritic shape. In other words, in the present specification, when the term "secondary particle layer" is used, a normal plating layer such as plating is also included. Further, the secondary particle layer may be a layer having one or more layers of roughened particles, may be a layer having one or more normal plating layers, or may be formed of one or more layers of roughened particles, respectively. The layer and the layer of the normal plating layer. Further, the surface treatment layer may have one or more layers other than the primary particle layer or the secondary particle layer. Further, the term "normal plating" refers to plating performed under the condition of a current density equal to or lower than the limiting current density.

此外，所謂一次粒子層是指包含直接形成在銅箔上的粗化粒子、及堆積在 該粗化粒子上的粗化粒子的層，所述堆積在該粗化粒子上的粗化粒子的組成與直接形成在銅箔上的粗化粒子相同、或具有與直接形成在銅箔上的粗化粒子所含有的元素相同的元素。所謂二次粒子層是指包含如下粗化粒子的層，所述粗化粒子形成在一次粒子層中所含的粗化粒子上，且其組成與形成一次粒子層的粗化粒子不同，或含有形成一次粒子層的粗化粒子所不含的元素。 In addition, the primary particle layer refers to a layer including roughened particles directly formed on a copper foil and roughened particles deposited on the roughened particles, and the composition of the roughened particles deposited on the roughened particles It is the same as the roughened particles directly formed on the copper foil, or has the same elements as those contained in the roughened particles directly formed on the copper foil. The secondary particle layer refers to a layer containing roughened particles formed on the roughened particles contained in the primary particle layer, and having a composition different from that of the roughened particles forming the primary particle layer, or containing An element which is not contained in the roughened particles of the primary particle layer.

另外，在無法測量構成所述一次粒子及/或二次粒子的元素的有無、及/或該元素的濃度或附著量的情況下，利用例如掃描式電子顯微鏡照片對一次粒子及二次粒子進行觀察時，可將看上去重疊且存在於銅箔側(下方)的粒子、及不重疊的粒子判定為一次粒子，將看上去重疊且存在於其他粒子上的粒子判定為二次粒子。此外，在銅箔上設置有銅等基底鍍覆層(正常鍍覆層)的情況下，所述「直接形成在銅箔上的粗化粒子」也包含直接形成在該基底鍍覆層上的粗化粒子。 In addition, when it is not possible to measure the presence or absence of an element constituting the primary particle and/or the secondary particle, and/or the concentration or adhesion amount of the element, the primary particle and the secondary particle are subjected to, for example, a scanning electron micrograph. At the time of observation, particles that appear to overlap and exist on the copper foil side (below) and particles that do not overlap can be determined as primary particles, and particles that appear to overlap and exist on other particles can be determined as secondary particles. Further, when a base plating layer (normal plating layer) such as copper is provided on the copper foil, the "roughened particles directly formed on the copper foil" also include the direct formation on the base plating layer. Coarse particles.

關於本發明的電池用表面處理銅箔，依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對表面處理層表面進行測量時的十點平均粗糙度Rz為1.8μm以上。若Rz小於1.8μm，則如圖1的概念圖所示，銅箔上的粗化粒子呈細長的樹枝狀分佈，該細長的樹枝狀粒子容易因外力而導致樹枝的一部分被折斷，或從根部脫落，因此與活性物質的密接性並不良好。另一方面，若Rz為1.8μm以上，則如圖2的概念圖所示，尖銳的立起消失，而生成帶有弧度的形狀的粒子，因此樹枝不易折斷，也不易從根部脫落。結果，與活性物質的密接性提高。就該觀點而言，十點平均粗糙度Rz更佳為1.9μm以上，更佳為2.0μm以上，進而更佳為2.1μm以上，進而更佳為2.2μm以上，進而更佳為2.3μm以上，進而更佳為2.35μm以上。十點平均粗糙度Rz的上限無需特別限定，典型為例如10μm以下，較佳為8μm以下，進而較佳為5μm以下，進而較佳為3.30μm以下，進而較佳為3.20μm以下，進而較佳為3.10μm以下，進而較佳為3.05 μm以下，進而較佳為3μm以下，進而較佳為2.95μm以下，進而較佳為2.90μm以下，進而較佳為2.85μm以下，進而較佳為2.80μm以下。在Rz為3μm以下等某程度小的情況下，推斷粗化粒子變得更不易脫落，與活性物質的密接性變得更良好。此外，在表面處理層存在於銅箔的兩面的情況下，只要一面的十點平均粗糙度Rz為所述範圍內，則發揮本發明的效果，因此將一面的十點平均粗糙度Rz設為所述範圍內即可，也可將兩面的十點平均粗糙度Rz設為所述範圍內。 In the surface-treated copper foil for a battery of the present invention, the ten-point average roughness Rz when the surface of the surface-treated layer is measured using a laser microscope having a wavelength of 405 nm is 1.8 μm or more in accordance with JIS B0601 1994. If Rz is less than 1.8 μm, as shown in the conceptual diagram of FIG. 1, the roughened particles on the copper foil are elongated and branched, and the elongated dendritic particles are easily broken due to external force, or from the root. Since it falls off, the adhesiveness with an active material is not favorable. On the other hand, when Rz is 1.8 μm or more, as shown in the conceptual diagram of Fig. 2, the sharp rise disappears and particles having a curved shape are formed, so that the branches are not easily broken and are not easily peeled off from the root. As a result, the adhesion to the active material is improved. From this viewpoint, the ten-point average roughness Rz is more preferably 1.9 μm or more, more preferably 2.0 μm or more, still more preferably 2.1 μm or more, still more preferably 2.2 μm or more, and still more preferably 2.3 μm or more. More preferably, it is 2.35 μm or more. The upper limit of the ten-point average roughness Rz is not particularly limited, and is typically, for example, 10 μm or less, preferably 8 μm or less, more preferably 5 μm or less, still more preferably 3.30 μm or less, still more preferably 3.20 μm or less, and further preferably It is 3.10 μm or less, more preferably 3.05 μm or less, further preferably 3 μm or less, further preferably 2.95 μm or less, further preferably 2.90 μm or less, further preferably 2.85 μm or less, and further preferably 2.80 μm. the following. When the Rz is a certain degree such as 3 μm or less, it is estimated that the roughened particles are less likely to fall off, and the adhesion to the active material is further improved. Further, when the surface treatment layer is present on both surfaces of the copper foil, if the ten-point average roughness Rz of one surface is within the above range, the effect of the present invention is exhibited. Therefore, the ten-point average roughness Rz of one surface is set to The range may be within the range, and the ten-point average roughness Rz of both sides may be set within the range.

此外，所述所謂「表面處理層表面」，在電池用表面處理銅箔具有一次粒子層、二次粒子層、耐熱層、防銹層、鉻酸鹽處理層、矽烷偶合處理層、鍍覆層等多層的情況下是指該多層的最外層的表面。 In addition, the surface treatment layer surface of the battery has a primary particle layer, a secondary particle layer, a heat-resistant layer, a rustproof layer, a chromate treatment layer, a decane coupling treatment layer, and a plating layer. In the case of a plurality of layers, it means the surface of the outermost layer of the multilayer.

另外，就所述相同的觀點而言，本發明的電池用表面處理銅箔較佳為將依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對表面處理層表面進行測量時的算術平均粗糙度Ra設為0.26μm以上。所述算術平均粗糙度Ra更佳為0.28μm以上，更佳為0.30μm以上，更佳為0.32μm以上，更佳為0.34μm以上，更佳為0.36μm以上，更佳為0.38μm以上，進而較佳為0.40μm以上。算術平均粗糙度Ra的上限無需特別限定，典型為例如5.0μm以下，較佳為4.5μm以下，進而較佳為4.0μm以下，進而較佳為3.5μm以下，進而較佳為3.0μm以下，進而較佳為2.5μm以下，進而較佳為2.0μm以下，進而較佳為1.5μm以下，進而較佳為1.0μm以下，進而較佳為0.5μm以下，進而較佳為0.45μm以下，進而較佳為0.44μm以下，進而較佳為0.41μm以下，進而較佳為0.40μm以下。此外，在表面處理層存在於銅箔的兩面的情況下，只要一面的算術平均粗糙度Ra為所述範圍內，則發揮本發明的效果，因此將一面的算術平均粗糙度Ra設為所述範圍內即可，也可將兩面的算術平均粗糙度Ra設為所述範圍內。 Further, from the same viewpoint, the surface-treated copper foil for a battery of the present invention preferably has an arithmetic mean roughness Ra when the surface of the surface-treated layer is measured using a laser microscope having a wavelength of 405 nm in accordance with JIS B0601 1994. It is set to 0.26 μm or more. The arithmetic mean roughness Ra is more preferably 0.28 μm or more, more preferably 0.30 μm or more, still more preferably 0.32 μm or more, still more preferably 0.34 μm or more, still more preferably 0.36 μm or more, and still more preferably 0.38 μm or more. It is preferably 0.40 μm or more. The upper limit of the arithmetic mean roughness Ra is not particularly limited, and is typically 5.0 μm or less, preferably 4.5 μm or less, more preferably 4.0 μm or less, further preferably 3.5 μm or less, further preferably 3.0 μm or less. It is preferably 2.5 μm or less, more preferably 2.0 μm or less, further preferably 1.5 μm or less, further preferably 1.0 μm or less, further preferably 0.5 μm or less, further preferably 0.45 μm or less, and further preferably It is 0.44 μm or less, more preferably 0.41 μm or less, further preferably 0.40 μm or less. In the case where the surface treatment layer is present on both surfaces of the copper foil, if the arithmetic mean roughness Ra of one surface is within the above range, the effect of the present invention is exhibited. Therefore, the arithmetic mean roughness Ra of one surface is set to the above. The range may be within the range, and the arithmetic mean roughness Ra of both faces may be set within the range.

較佳為將所述一次粒子層的平均粒徑設為0.1~0.6μm。另外，較佳為將二次粒子層的平均粒徑設為0.01~0.45μm。此處所謂粒徑是指在利用 掃描式電子顯微鏡從銅箔的正上方拍攝照片而觀察粗化粒子的情況下包圍該粒子的最小圓的直徑。另外，所謂平均粒徑是指多個粗化粒子的粒徑的算術平均值。具體而言，所述一次粒子層的平均粒徑是指在利用所述掃描式電子顯微鏡所拍攝的照片中存在於橫4μm×縱3μm的區域的一次粒子層的粗化粒子的粒徑的算術平均值。另外，所述二次粒子層的平均粒徑是指在利用所述掃描式電子顯微鏡所拍攝的照片中存在於橫4μm×縱3μm的區域的二次粒子層的粗化粒子的粒徑的算術平均值。 Preferably, the average particle diameter of the primary particle layer is set to 0.1 to 0.6 μm. Further, it is preferred that the average particle diameter of the secondary particle layer be 0.01 to 0.45 μm. The particle diameter herein refers to the diameter of the smallest circle surrounding the particles when a photograph is taken from the directly above the copper foil by a scanning electron microscope to observe the roughened particles. In addition, the average particle diameter means the arithmetic mean value of the particle diameter of a plurality of roughened particles. Specifically, the average particle diameter of the primary particle layer refers to arithmetic of the particle diameter of the roughened particles of the primary particle layer existing in a region of 4 μm × 3 μm in the image taken by the scanning electron microscope. average value. In addition, the average particle diameter of the secondary particle layer refers to the arithmetic of the particle diameter of the roughened particles of the secondary particle layer existing in the region of 4 μm × 3 μm in the image taken by the scanning electron microscope. average value.

此外，一次粒子層的平均粒徑可通過在形成一次粒子層時降低所使用的鍍覆液中的利用鍍覆附著在銅箔的元素的濃度、及/或提高電流密度、及/或延長表面處理時間(進行鍍覆時的通電時間)、及/或增加鍍覆次數等而變大。另外，一次粒子層的平均粒徑可通過在形成一次粒子層時提高所使用的鍍覆液中的利用鍍覆附著在銅箔的元素的濃度、及/或降低電流密度、及/或縮短表面處理時間(進行鍍覆時的通電時間)、及/或減少鍍覆次數等而變小。 Further, the average particle diameter of the primary particle layer can reduce the concentration of the element attached to the copper foil by plating, and/or increase the current density, and/or extend the surface in the plating solution used when forming the primary particle layer. The processing time (the energization time at the time of plating), and/or the increase in the number of platings, etc., become large. Further, the average particle diameter of the primary particle layer can increase the concentration of the element adhered to the copper foil by plating in the plating solution used when forming the primary particle layer, and/or reduce the current density, and/or shorten the surface. The processing time (the energization time at the time of plating), and/or the reduction in the number of platings, etc., become small.

另外，二次粒子層的平均粒徑可通過在形成二次粒子層時降低所使用的鍍覆液中的利用鍍覆附著在銅箔的元素的濃度、及/或提高電流密度、及/或延長表面處理時間(進行鍍覆時的通電時間)、及/或增加鍍覆次數等而變大。另外，二次粒子層的平均粒徑可通過在形成二次粒子層時提高所使用的鍍覆液中的利用鍍覆附著在銅箔的元素的濃度、及/或降低電流密度、及/或縮短表面處理時間(進行鍍覆時的通電時間)、及/或減少鍍覆次數等而變小。 Further, the average particle diameter of the secondary particle layer can reduce the concentration of the element adhering to the copper foil by plating in the plating solution used, and/or increase the current density, and/or when forming the secondary particle layer. The surface treatment time (the energization time at the time of plating) is extended, and/or the number of plating times is increased to become large. Further, the average particle diameter of the secondary particle layer can increase the concentration of the element adhered to the copper foil by plating in the plating solution used, and/or decrease the current density, and/or when forming the secondary particle layer. The surface treatment time (the energization time at the time of plating) is shortened, and/or the number of times of plating is reduced, and the like.

本發明的電池用表面處理銅箔的表面處理層中的一次粒子層可具有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種或兩種以上的元素。表面處理層中的一次粒子層較佳具有選自由Cu、W、Ti、As、Cr及P所組成的群中的一種以上的元素。表面處理層中的一次粒子層較佳具有選自由Cu、W、As及P所組成的群中的一種以上的元素。其原因 在於，變得更容易防止粉體脫落。另外，關於二次粒子層，也可具有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種或兩種以上的元素。而且，所述一次粒子層及二次粒子層中所含的選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上的元素的合計附著量例如可設為100μg/dm²以上。合計附著量的上限也無特別限制，例如可設為10000μg/dm²以下。另外，所述一次粒子層及二次粒子層中所含的選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種或兩種以上的元素的合計附著量例如可設為100μg/dm²以上。合計附著量的上限也無特別限制，例如可設為10000μg/dm²以下。 The primary particle layer in the surface treatment layer of the surface-treated copper foil for a battery of the present invention may have a group selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. One or two or more elements. The primary particle layer in the surface treatment layer preferably has one or more elements selected from the group consisting of Cu, W, Ti, As, Cr, and P. The primary particle layer in the surface treatment layer preferably has one or more elements selected from the group consisting of Cu, W, As, and P. The reason for this is that it becomes easier to prevent the powder from falling off. Further, the secondary particle layer may have one or two or more elements selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. Further, one or more selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn contained in the primary particle layer and the secondary particle layer The total adhesion amount of the elements can be, for example, 100 μg/dm ² or more. The upper limit of the total amount of adhesion is not particularly limited, and may be, for example, 10000 μg/dm ² or less. Further, the primary particle layer and the secondary particle layer are one or two selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. The total adhesion amount of the above elements may be, for example, 100 μg/dm ² or more. The upper limit of the total amount of adhesion is not particularly limited, and may be, for example, 10000 μg/dm ² or less.

就提高電池容量的觀點而言，關於電極活性物質，從單純的碳系活性物質研究到矽系或混合有多種的複合系活性物質。在使用此種矽系活性物質的情況下，有使用聚醯亞胺系黏合劑的情況，接合時必須進行300℃以上的加熱。因此，雖然只要與活性物質的密接性良好就能夠達成本發明的目的，但更佳為也具有在300℃以上的加熱後也不會產生銅箔表面的氧化變色的耐熱特性的二次電池集電體用銅箔。通過從所述Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中選擇一種或兩種以上的元素，依照所述附著量形成二次粒子層，能夠提高所述耐熱特性。 From the viewpoint of improving the battery capacity, the electrode active material is studied from a simple carbon-based active material to a lanthanide-based or mixed composite active material. When such a quinone-based active material is used, when a polyimide-based adhesive is used, it is necessary to perform heating at 300 ° C or higher during bonding. Therefore, although the object of the present invention can be attained as long as the adhesion to the active material is good, it is more preferable to have a secondary battery set which does not cause oxidative discoloration on the surface of the copper foil after heating at 300 ° C or higher. Copper foil for electrics. By selecting one or two or more elements from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn, forming secondary particles according to the adhesion amount The layer can improve the heat resistance characteristics.

本發明的電池用表面處理銅箔有表面處理層不含Ni的情況、或表面處理層含有Ni的情況。在表面處理層含有Ni的情況下，表面處理層的Ni的附著量較佳為100μg/dm²以上。若該Ni的附著量低於100μg/dm²，則有產生耐熱性明顯劣化的問題的情況。在表面處理層含有Ni的情況下，表面處理層的Ni的附著量較佳為4500μg/dm²以下。若超過4500μg/dm²，則Ni膜厚變厚，由此有產生如下問題的擔憂：電阻值上升而導致作為集電體用銅箔的電氣特性降低。該Ni的附著量更佳為200μg/dm²以上，進而較佳為300μg/dm²以上，進而較佳為 400μg/dm²以上。另外，該Ni的附著量更佳為4400μg/dm²以下，進而較佳為4300μg/dm²以下，進而較佳為4200μg/dm²以下，進而較佳為4100μg/dm²以下，進而較佳為4000μg/dm²以下，進而較佳為3950μg/dm²以下。此外，在表面處理層含有Ni的情況下，有發揮如下效果的情況：與不含Ni的情況相比，表面處理銅箔的耐化學品性提高。 The surface-treated copper foil for a battery of the present invention may have a case where the surface treatment layer does not contain Ni or a surface treatment layer contains Ni. When the surface treatment layer contains Ni, the amount of Ni deposited on the surface treatment layer is preferably 100 μg/dm ² or more. When the adhesion amount of Ni is less than 100 μg/dm ² , there is a problem that heat resistance is significantly deteriorated. When the surface treatment layer contains Ni, the amount of Ni deposited on the surface treatment layer is preferably 4,500 μg/dm ² or less. When the thickness is more than 4,500 μg/dm ² , the thickness of the Ni film is increased, which causes a problem that the electrical resistance of the copper foil as a current collector is lowered due to an increase in the electric resistance value. The amount of adhesion of Ni is more preferably 200 μg/dm ² or more, still more preferably 300 μg/dm ² or more, and still more preferably 400 μg/dm ² or more. Further, the Ni deposition amount is more preferably 4400μg / dm ² or less, and further preferably 4300μg / dm ² or less, and further preferably 4200μg / dm ² or less, and further preferably 4100μg / dm ² or less, and further preferably It is 4000 μg/dm ² or less, and more preferably 3950 μg/dm ² or less. Further, when the surface treatment layer contains Ni, there is a case where the chemical resistance of the surface-treated copper foil is improved as compared with the case where Ni is not contained.

本發明的電池用表面處理銅箔有表面處理層不含Co的情況、或表面處理層含有Co的情況。在表面處理層含有Co的情況下，表面處理層的Co的附著量較佳為100μg/dm²以上。若該Co的附著量低於100μg/dm²，則有產生耐熱性明顯劣化的問題的情況。另外，在表面處理層含有Co的情況下，表面處理層的Co的附著量較佳為6000μg/dm²以下。若超過6000μg/dm²，則Co膜厚變厚，由此有產生如下問題的擔憂：表現出磁性而導致作為電池用銅箔、尤其是作為集電體用銅箔的電氣特性變差。該Co的附著量更佳為200μg/dm²以上，更佳為300μg/dm²以上，更佳為400μg/dm²以上，更佳為500μg/dm²以上，更佳為600μg/dm²以上，更佳為700μg/dm²以上，更佳為800μg/dm²以上，更佳為900μg/dm²以上，更佳為1000μg/dm²以上。另外，該Co的附著量更佳為5500μg/dm²以下，更佳為5000μg/dm²以下，更佳為4500μg/dm²以下，更佳為4300μg/dm²以下，更佳為4200μg/dm²以下，更佳為4100μg/dm²以下，更佳為4000μg/dm²以下，更佳為3950μg/dm²以下。此外，在表面處理層含有Co的情況下，有發揮如下效果的情況：與不含Co的情況相比，表面處理銅箔的耐候性提高。 The surface-treated copper foil for a battery of the present invention may have a case where the surface treatment layer does not contain Co or a surface treatment layer contains Co. When the surface treatment layer contains Co, the amount of Co deposited on the surface treatment layer is preferably 100 μg/dm ² or more. When the adhesion amount of Co is less than 100 μg/dm ² , there is a problem that heat resistance is remarkably deteriorated. Further, when the surface treatment layer contains Co, the amount of Co deposited on the surface treatment layer is preferably 6000 μg/dm ² or less. When it exceeds 6000 μg/dm ² , the thickness of the Co film becomes thick, and there is a concern that the magnetic properties are exhibited, and the electrical characteristics of the copper foil for a battery, particularly the copper foil for a current collector, are deteriorated. The adhesion amount of Co is more preferably 200 μg/dm ² or more, more preferably 300 μg/dm ² or more, still more preferably 400 μg/dm ² or more, still more preferably 500 μg/dm ² or more, still more preferably 600 μg/dm ² or more. more preferably 700μg / dm ² or more, more preferably 800μg / dm ² or more, more preferably 900μg / dm ² or more, more preferably 1000μg / dm ² or more. Further, the deposition amount of Co is more preferably 5500μg / dm ² or less, more preferably 5000μg / dm ² or less, more preferably 4500μg / dm ² or less, more preferably 4300μg / dm ² or less, more preferably 4200μg / dm ² Hereinafter, it is more preferably 4100 μg/dm ² or less, still more preferably 4000 μg/dm ² or less, still more preferably 3950 μg/dm ² or less. In addition, when Co is contained in the surface treatment layer, there is a case where the weather resistance of the surface-treated copper foil is improved as compared with the case where Co is not contained.

此外，在本發明中，規定表面處理層的Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、Sn、P等元素的附著量，但其是規定存在於包含一次粒子層及二次粒子層的表面處理層的元素的附著量的總量。另外，在這些表面處理層存在於銅箔的兩個面的情況下，是對其中一個面的表面處理層的規定，而非形成在兩個面的表面處理層中含有的元素(例如Ni等)的合計值。 Further, in the present invention, the adhesion amount of elements such as Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, Sn, and P in the surface treatment layer is specified, but it is prescribed to exist in the primary particles. The total amount of the adhesion of the elements of the surface treatment layer of the layer and the secondary particle layer. Further, in the case where these surface treatment layers are present on both faces of the copper foil, the surface treatment layer of one of the faces is specified, and the elements contained in the surface treatment layer formed on both faces (for example, Ni, etc.) The total value of ).

關於本發明的電池用表面處理銅箔的表面處理層，只要Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、Sn、P等元素的附著量為所述範圍內，則可視需要變更這些元素的種類及附著量，但就進一步提高與活性物質薄膜的密接性的觀點而言，較佳為一次粒子層由Cu構成。此處，「一次粒子層由Cu構成」的概念包括「一次粒子層僅含有Cu」、及「一次粒子層僅含有Cu及不可避免的雜質」。另外，就提高表面處理銅箔的耐熱性的觀點而言，較佳為二次粒子層由Cu、Co、Ni構成。此處，「二次粒子層由Cu、Co、Ni構成」的概念包括「二次粒子層僅含有Cu、Co及Ni」、及「二次粒子層僅含有Cu、Co及Ni以及不可避免的雜質」。 In the surface treatment layer of the surface-treated copper foil for a battery of the present invention, as long as the adhesion amount of elements such as Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, Sn, and P is within the above range, The type and amount of these elements may be changed as needed. However, from the viewpoint of further improving the adhesion to the active material film, the primary particle layer is preferably made of Cu. Here, the concept of "the primary particle layer is composed of Cu" includes "the primary particle layer contains only Cu", and "the primary particle layer contains only Cu and unavoidable impurities". Moreover, from the viewpoint of improving the heat resistance of the surface-treated copper foil, it is preferred that the secondary particle layer be composed of Cu, Co, and Ni. Here, the concept of "the secondary particle layer is composed of Cu, Co, and Ni" includes "the secondary particle layer contains only Cu, Co, and Ni", and "the secondary particle layer contains only Cu, Co, and Ni, and is inevitable. Impurities."

此外，表面處理層所含有的元素的附著量可通過在形成表面處理層時提高所使用的表面處理液中的該元素的濃度，及/或在表面處理為鍍覆的情況下提高電流密度，及/或延長表面處理時間(進行鍍覆時的通電時間)等而變多。另外，表面處理層所含有的元素的附著量可通過在形成表面處理層時降低所使用的表面處理液中的該元素的濃度，及/或在表面處理為鍍覆的情況下降低電流密度，及/或縮短表面處理時間(進行鍍覆時的通電時間)等而變少。 Further, the amount of the element contained in the surface treatment layer can be increased by increasing the concentration of the element in the surface treatment liquid used when forming the surface treatment layer, and/or increasing the current density in the case where the surface treatment is plating. And/or prolonging the surface treatment time (the energization time at the time of plating) and the like. Further, the amount of the element contained in the surface treatment layer can be lowered by lowering the concentration of the element in the surface treatment liquid used when the surface treatment layer is formed, and/or reducing the current density in the case where the surface treatment is plating. And/or shortening the surface treatment time (the energization time at the time of plating) and the like.

<一次粒子層、二次粒子層的形成條件> <Formation conditions of primary particle layer and secondary particle layer>

本發明的電池用表面處理銅箔的表面處理層是從銅箔的表面側依序形成一次粒子層及二次粒子層。一次粒子層及二次粒子層可從銅箔的表面側直接形成，也可在銅箔的表面側形成基底鍍覆層，接著依序形成一次粒子層及二次粒子層。所述基底鍍覆層也可為鍍Cu層。以下表示一次粒子層、二次粒子層的形成條件，但其只不過是表示較佳例，只要依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對表面處理層表面進行測量時的十點平均粗糙度Rz為1.8μm以上，則也可為下述所示以外的鍍覆條件。 In the surface-treated layer of the surface-treated copper foil for a battery of the present invention, a primary particle layer and a secondary particle layer are sequentially formed from the surface side of the copper foil. The primary particle layer and the secondary particle layer may be formed directly from the surface side of the copper foil, or a base plating layer may be formed on the surface side of the copper foil, and then the primary particle layer and the secondary particle layer may be sequentially formed. The base plating layer may also be a Cu plating layer. The conditions for forming the primary particle layer and the secondary particle layer are shown below, but it is merely a preferred example, as long as the ten-point average roughness of the surface of the surface treated layer is measured using a laser microscope having a wavelength of 405 nm in accordance with JIS B0601 1994. When the degree Rz is 1.8 μm or more, plating conditions other than those shown below may be employed.

此外，依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對表面處理層 表面進行測量時的十點平均粗糙度Rz可通過在形成一次粒子層及/或二次粒子層時降低所使用的鍍覆液中的利用鍍覆附著在銅箔的元素的濃度、及/或提高電流密度、及/或延長表面處理時間(進行鍍覆時的通電時間)、及/或增加鍍覆次數等而變大。另外，依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對表面處理層表面進行測量時的十點平均粗糙度Rz可在形成一次粒子層及/或二次粒子層時提高所使用的表面處理液中利用鍍覆附著在銅箔的元素的濃度、及/或降低電流密度、及/或縮短表面處理時間(進行鍍覆時的通電時間)等而變小。 Further, according to JIS B0601 1994, the ten-point average roughness Rz when the surface of the surface treatment layer is measured using a laser microscope having a wavelength of 405 nm can reduce the plating used when forming the primary particle layer and/or the secondary particle layer. In the liquid, the concentration of the element adhered to the copper foil by the plating, and/or the increase in the current density, and/or the extension of the surface treatment time (the energization time during the plating), and/or the increase in the number of plating times, etc., become large. . Further, according to JIS B0601 1994, the ten-point average roughness Rz when measuring the surface of the surface treatment layer using a laser microscope having a wavelength of 405 nm can improve the surface treatment liquid used when forming the primary particle layer and/or the secondary particle layer. The concentration of the element adhered to the copper foil by plating and/or the current density is lowered, and/or the surface treatment time (the energization time at the time of plating) is shortened.

另外，依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對表面處理層表面進行測量時的算術平均粗糙度Ra可通過在形成一次粒子層及/或二次粒子層時降低所使用的鍍覆液中的利用鍍覆附著在銅箔的元素的濃度、及/或提高電流密度、及/或延長表面處理時間(進行鍍覆時的通電時間)等而變大。另外，依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對表面處理層表面進行測量時的算術平均粗糙度Ra可通過在形成一次粒子層及/或二次粒子層時提高所使用的鍍覆液中的利用鍍覆附著在銅箔的元素的濃度、及/或降低電流密度、及/或縮短表面處理時間(進行鍍覆時的通電時間)、及/或減少鍍覆次數等而變小。 Further, according to JIS B0601 1994, the arithmetic mean roughness Ra when measuring the surface of the surface treatment layer using a laser microscope having a wavelength of 405 nm can reduce the plating liquid used when forming the primary particle layer and/or the secondary particle layer. The concentration of the element adhered to the copper foil by plating, and/or the increase in current density, and/or the extension of the surface treatment time (the energization time at the time of plating) become large. Further, according to JIS B0601 1994, the arithmetic mean roughness Ra when measuring the surface of the surface treatment layer using a laser microscope having a wavelength of 405 nm can improve the plating liquid used when forming the primary particle layer and/or the secondary particle layer. The concentration of the element adhered to the copper foil by plating, and/or the reduction of the current density, and/or the reduction of the surface treatment time (the energization time at the time of plating), and/or the reduction in the number of platings, etc., become small.

‧一次粒子層 ‧ primary particle layer

在利用一次粒子鍍覆液(A)進行處理後，利用一次粒子鍍覆液(B)進行處理的情況下，能夠在以下的條件下形成一次粒子層。 When the primary particle plating solution (B) is used for the treatment by the primary particle plating solution (A), the primary particle layer can be formed under the following conditions.

(利用一次粒子鍍覆液(A)的處理) (Using primary particle plating solution (A) treatment)

<電解液組成> <electrolyte composition>

銅：5~15g/L Copper: 5~15g/L

硫酸：70~80g/L Sulfuric acid: 70~80g/L

<製造條件> <Manufacturing conditions>

電流密度：40~60A/dm² Current density: 40~60A/dm ²

電解液溫度：25~35℃ Electrolyte temperature: 25~35°C

電解時間：0.5~1.6秒 Electrolysis time: 0.5~1.6 seconds

(利用一次粒子鍍覆液(B)的處理) (Using primary particle plating solution (B) treatment)

<電解液組成> <electrolyte composition>

銅：20~50g/L Copper: 20~50g/L

硫酸：60~100g/L Sulfuric acid: 60~100g/L

<製造條件> <Manufacturing conditions>

電流密度：4~10A/dm² Current density: 4~10A/dm ²

電解液溫度：35~55℃ Electrolyte temperature: 35~55°C

電解時間：1.4~2.5秒 Electrolysis time: 1.4~2.5 seconds

在僅通過利用一次粒子鍍覆液(I)的處理形成一次粒子層的情況下，能夠在以下的利用一次粒子鍍覆液(I)的處理1或利用一次粒子鍍覆液(I)的處理2所記載的條件下實施。 When the primary particle layer is formed only by the treatment using the primary particle plating solution (I), the following treatment using the primary particle plating solution (I) or the treatment using the primary particle plating solution (I) can be employed. Implemented under the conditions described in 2.

(利用一次粒子鍍覆液(I)的處理1) (Processing using primary particle plating solution (I) 1)

<電解液組成> <electrolyte composition>

銅：10~45g/L Copper: 10~45g/L

鈷：5~30g/L Cobalt: 5~30g/L

鎳：5~30g/L Nickel: 5~30g/L

pH值：2.8~3.2 pH: 2.8~3.2

<製造條件> <Manufacturing conditions>

電流密度：30~45A/dm² Current density: 30~45A/dm ²

電解液溫度：30~40℃ Electrolyte temperature: 30~40°C

電解時間：0.3~0.8秒 Electrolysis time: 0.3~0.8 seconds

(利用一次粒子鍍覆液(I)的處理2) (Using primary particle plating solution (I) treatment 2)

<電解液組成> <electrolyte composition>

銅：5~15g/L Copper: 5~15g/L

鎳：3~30g/L Nickel: 3~30g/L

pH值：2.6~3.0 pH: 2.6~3.0

<製造條件> <Manufacturing conditions>

電流密度：50~70A/dm² Current density: 50~70A/dm ²

電解液溫度：30~40℃ Electrolyte temperature: 30~40°C

電解時間：0.3~0.9秒 Electrolysis time: 0.3~0.9 seconds

‧二次粒子層 ‧ secondary particle layer

在形成二次粒子層的情況下，能夠通過以下的利用二次粒子鍍覆液(I)或二次粒子鍍覆液(II)的處理來實施。 When the secondary particle layer is formed, it can be carried out by the following treatment using the secondary particle plating solution (I) or the secondary particle plating solution (II).

(利用二次粒子鍍覆液(I)的處理) (Using secondary particle plating solution (I) treatment)

<電解液組成> <electrolyte composition>

銅：10~15g/L Copper: 10~15g/L

鈷：5~15g/L Cobalt: 5~15g/L

鎳：5~15g/L Nickel: 5~15g/L

pH值：2.8~3.2 pH: 2.8~3.2

<製造條件> <Manufacturing conditions>

電流密度：20~40A/dm² Current density: 20~40A/dm ²

電解液溫度：33~37℃ Electrolyte temperature: 33~37°C

電解時間：0.5~1.0秒 Electrolysis time: 0.5~1.0 seconds

(利用二次粒子鍍覆液(II)的處理) (Using secondary particle plating solution (II) treatment)

<電解液組成> <electrolyte composition>

銅：5~12g/L Copper: 5~12g/L

鎳：2~11g/L Nickel: 2~11g/L

pH值：2.8 pH: 2.8

<製造條件> <Manufacturing conditions>

電流密度：55~65A/dm² Current density: 55 ~ 65A / dm ²

電解液溫度：35~40℃ Electrolyte temperature: 35~40°C

電解時間：0.3~0.9秒 Electrolysis time: 0.3~0.9 seconds

<覆蓋鍍覆> <cover plating>

可在二次粒子層上進行覆蓋鍍覆。通過形成覆蓋鍍覆，能夠期待耐熱性的提高效果。通過覆蓋鍍覆所形成的層例如可列舉：Zn-Cr合金層、Ni-Mo合金層、Zn層、Co-Mo合金層、Co-Ni合金層、Ni-W合金層、Ni-Zn合金層、Ni-P合金層、Ni-Fe合金層、Ni-Al合金層、Co-Zn合金層、Co-P合金層、Zn-Co合金層、Ni層、Co層、Cr層、Al層、Sn層、Sn-Ni層、Ni-Sn層或Zn-Ni合金層等之類的由選自由Zn、Cr、Ni、Fe、Ta、Cu、Al、P、W、Mn、Sn、As、Ti、Mo及Co等所組成的群中的一種元素所構成的金屬層、或含有選自由Zn、Cr、Ni、Fe、Ta、Cu、Al、P、W、Mn、Sn、As、Ti、Mo及Co所組成的群中的2種或3種以上的合金層或由選自所述元素群中的2種或3種以上的元素所構成的合金層。 Cover plating may be performed on the secondary particle layer. By forming a cover plating, the effect of improving heat resistance can be expected. Examples of the layer formed by the overcoat plating include a Zn—Cr alloy layer, a Ni—Mo alloy layer, a Zn layer, a Co—Mo alloy layer, a Co—Ni alloy layer, a Ni—W alloy layer, and a Ni—Zn alloy layer. , Ni-P alloy layer, Ni-Fe alloy layer, Ni-Al alloy layer, Co-Zn alloy layer, Co-P alloy layer, Zn-Co alloy layer, Ni layer, Co layer, Cr layer, Al layer, Sn a layer selected from the group consisting of Zn, Cr, Ni, Fe, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, and the like. a metal layer composed of one element selected from the group consisting of Mo and Co, or containing Zn, Cr, Ni, Fe, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, Mo, and Two or more alloy layers of the group consisting of Co or an alloy layer composed of two or more elements selected from the group of elements.

覆蓋鍍覆能夠通過進行以下的利用覆蓋鍍覆液等的處理、或將這些加以組合而實施。另外，無法通過濕式鍍覆設置的金屬層、及/或合金層能夠通過濺 鍍、物理蒸鍍(PVD)、化學蒸鍍(CVD)等乾式鍍覆法來設置。 The cover plating can be carried out by performing the following treatment with a plating solution or the like, or by combining these. Further, the metal layer and/or the alloy layer which cannot be provided by wet plating can be provided by a dry plating method such as sputtering, physical vapor deposition (PVD) or chemical vapor deposition (CVD).

‧利用覆蓋鍍覆液的處理(1)Zn-Cr ‧Use of cover plating solution (1) Zn-Cr

液體組成：重鉻酸鉀1~10g/L、Zn0.1~5g/L Liquid composition: potassium dichromate 1~10g/L, Zn0.1~5g/L

液溫：40~60℃ Liquid temperature: 40~60°C

pH值：0.5~10 pH: 0.5~10

電流密度：0.01~2.6A/dm² Current density: 0.01~2.6A/dm ²

通電時間：0.05~30秒 Power-on time: 0.05~30 seconds

‧利用覆蓋鍍覆液的處理(2)Ni-Mo ‧Using cover plating solution (2)Ni-Mo

液體組成：硫酸鎳270~280g/L、氯化鎳35~45g/L、乙酸鎳10~20g/L、鉬酸鈉1~60g/L、檸檬酸三鈉10~50g/L、十二烷基硫酸鈉50~90ppm Liquid composition: nickel sulfate 270~280g/L, nickel chloride 35~45g/L, nickel acetate 10~20g/L, sodium molybdate 1~60g/L, trisodium citrate 10~50g/L, dodecane Sodium sulfate 50~90ppm

液溫：20~65℃ Liquid temperature: 20~65°C

pH值：4~12 pH: 4~12

電流密度：0.5~5A/dm² Current density: 0.5~5A/dm ²

通電時間：0.1~5秒 Power-on time: 0.1~5 seconds

‧利用覆蓋鍍覆液的處理(3)Zn ‧Use of cover plating solution (3)Zn

液體組成：Zn1~15g/L Liquid composition: Zn1~15g/L

液溫：25~50℃ Liquid temperature: 25~50°C

pH值：2~6 pH: 2~6

電流密度：0.5~5A/dm² Current density: 0.5~5A/dm ²

通電時間：0.01~0.3秒 Power-on time: 0.01~0.3 seconds

‧利用覆蓋鍍覆液的處理(4)Co-Mo ‧Handling with cover plating solution (4)Co-Mo

液體組成：Co1~20g/L、鉬酸鈉1~60g/L、檸檬酸鈉10~110g/L Liquid composition: Co1~20g/L, sodium molybdate 1~60g/L, sodium citrate 10~110g/L

液溫：25~50℃ Liquid temperature: 25~50°C

pH值：5~7 pH: 5~7

電流密度：1~4A/dm² Current density: 1~4A/dm ²

通電時間：0.1~5秒 Power-on time: 0.1~5 seconds

‧利用覆蓋鍍覆液的處理(5)Co-Ni ‧Handling with cover plating solution (5)Co-Ni

液體組成：Co1~20g/L、Ni1~20g/L Liquid composition: Co1~20g/L, Ni1~20g/L

液溫：30~80℃ Liquid temperature: 30~80°C

pH值：1.5~3.5 pH: 1.5~3.5

電流密度：1~20A/dm² Current density: 1~20A/dm ²

通電時間：0.1~4秒 Power-on time: 0.1~4 seconds

‧利用覆蓋鍍覆液的處理(6)Zn-Ni ‧Using cover plating solution (6)Zn-Ni

液體組成：Zn1~30g/L、Ni1~30g/L Liquid composition: Zn1~30g/L, Ni1~30g/L

液溫：40~50℃ Liquid temperature: 40~50°C

pH值：2~5 pH: 2~5

電流密度：0.5~5A/dm² Current density: 0.5~5A/dm ²

通電時間：0.01~0.3秒 Power-on time: 0.01~0.3 seconds

‧利用覆蓋鍍覆液的處理(7)Ni-W ‧Using cover plating solution (7)Ni-W

液體組成：Ni1~30g/L、W1~300mg/L Liquid composition: Ni1~30g/L, W1~300mg/L

液溫：30~50℃ Liquid temperature: 30~50°C

pH值：2~5 pH: 2~5

電流密度：0.1~5A/dm² Current density: 0.1~5A/dm ²

通電時間：0.01~0.3秒 Power-on time: 0.01~0.3 seconds

‧利用覆蓋鍍覆液的處理(8)Ni-P ‧Using cover plating solution (8)Ni-P

液體組成：Ni1~30g/L、P1~10g/L Liquid composition: Ni1~30g/L, P1~10g/L

液溫：30~50℃ Liquid temperature: 30~50°C

pH值：2~5 pH: 2~5

電流密度：0.1~5A/dm² Current density: 0.1~5A/dm ²

通電時間：0.01~0.3秒 Power-on time: 0.01~0.3 seconds

<其他表面處理> <Other surface treatment>

另外，本發明的電池用表面處理銅箔的表面處理層也可在二次粒子層或所述覆蓋鍍覆層上進而具有選自由耐熱層、防銹層、鉻酸鹽處理層、矽烷偶合處理層、鍍覆層、樹脂層所組成的群中的1種以上的層。此外，所述耐熱層、防銹層、鉻酸鹽處理層、矽烷偶合處理層、鍍覆層、樹脂層也可分別形成多層(例如2層以上、3層以上等)。 Further, the surface treatment layer of the surface-treated copper foil for a battery of the present invention may further have a heat treatment layer, a rust preventive layer, a chromate treatment layer, and a decane coupling treatment on the secondary particle layer or the cover plating layer. One or more layers of the group consisting of a layer, a plating layer, and a resin layer. Further, the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, the decane coupling treatment layer, the plating layer, and the resin layer may be formed in multiple layers (for example, two or more layers, three or more layers, or the like).

作為耐熱層、防銹層，可使用公知的耐熱層、防銹層。例如耐熱層及/或防銹層可為含有選自鎳、鋅、錫、鈷、鉬、銅、鎢、磷、砷、鉻、釩、鈦、鋁、金、銀、鉑族元素、鐵、鉭的群中的1種以上的元素的層，也可為由選自鎳、鋅、錫、鈷、鉬、銅、鎢、磷、砷、鉻、釩、鈦、鋁、金、銀、鉑族元素、鐵、鉭的群中的1種以上的元素所構成的金屬層或合金層。另外，耐熱層及/或防銹層也可包含含有所述元素的氧化物、氮化物、矽化物。另外，耐熱層及/或防銹層也可為含有鎳-鋅合金的層。另外，耐熱層及/或防銹層也可為鎳-鋅合金層。所述鎳-鋅合金層也可除含有不可避免的雜質以外，還含有50 wt%~99wt%的鎳、50wt%~1wt%的鋅。所述鎳-鋅合金層的鋅及鎳的合計附著量也可為5~1000mg/m²、較佳為10~500mg/m²、較佳為20~100mg/m²。另外，所述含有鎳-鋅合金的層或所述鎳-鋅合金層的鎳的附著量與鋅的附著量的比(=鎳的附著量/鋅的附著量)較佳為1.5~10。另外，所述含有鎳-鋅合金的層或所述鎳-鋅合金層的鎳的附著量較佳為0.5mg/m²~500mg/m²，更佳為1mg/m²~50mg/m²。在耐熱層及/或防銹層為含有鎳-鋅合金的層的情況下，通孔或導孔等的內壁部與去汙液接觸時，銅箔與樹脂基板的界面不易被去汙液腐蝕，銅箔與樹脂基板的密接性提高。 As the heat-resistant layer and the rust-preventive layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat resistant layer and/or the rustproof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, The layer of one or more elements in the group of cerium may also be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum. A metal layer or an alloy layer composed of one or more elements of a group of elements, iron, and lanthanum. Further, the heat-resistant layer and/or the rust-preventive layer may contain an oxide, a nitride, or a telluride containing the element. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat resistant layer and/or the rustproof layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain, in addition to unavoidable impurities, 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , preferably 20 to 100 mg/m ² . Further, the ratio of the amount of adhesion of nickel to the nickel-zinc alloy layer or the nickel-zinc alloy layer to the amount of adhesion of zinc (=the amount of adhesion of nickel/the amount of adhesion of zinc) is preferably 1.5 to 10. Further, the adhesion amount of the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer is preferably 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ^{2 .} . When the heat-resistant layer and/or the rust-preventive layer is a layer containing a nickel-zinc alloy, when the inner wall portion of the through hole or the guide hole or the like is in contact with the decontamination liquid, the interface between the copper foil and the resin substrate is not easily decontaminated. Corrosion, the adhesion between the copper foil and the resin substrate is improved.

例如耐熱層及/或防銹層可為依序積層附著量為1mg/m²~100mg/m²、較佳為5mg/m²~50mg/m²的鎳或鎳合金層與附著量為1mg/m²~80mg/m²、較佳為5mg/m²~40mg/m²的錫層而成的層，所述鎳合金層也可由鎳-鉬合金、鎳-鋅合金、鎳-鉬-鈷合金、鎳-錫合金的任一種構成。 For example, the heat-resistant layer and/or the rust-preventing layer may be a nickel or nickel alloy layer having a deposition amount of 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and an adhesion amount of 1 mg. a layer of /m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ^{2 of} a tin layer, which may also be a nickel-molybdenum alloy, a nickel-zinc alloy, or a nickel-molybdenum- Any of a cobalt alloy and a nickel-tin alloy.

本說明書中，所謂鉻酸鹽處理層是指利用含有鉻酸酐、鉻酸、二鉻酸、鉻酸鹽或二鉻酸鹽的液體處理過的層。鉻酸鹽處理層也可含有Co、Fe、Ni、Mo、Zn、Ta、Cu、Al、P、W、Sn、As及Ti等元素(可為金屬、合金、氧化物、氮化物、硫化物等任意形態)。作為鉻酸鹽處理層的具體例，可列舉利用鉻酸酐或二鉻酸鉀水溶液處理過的鉻酸鹽處理層、或利用含有鉻酸酐或二鉻酸鉀及鋅的處理液處理過的鉻酸鹽處理層等。 In the present specification, the chromate treatment layer means a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may also contain elements such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As, and Ti (may be metals, alloys, oxides, nitrides, sulfides) Any form). Specific examples of the chromate-treated layer include a chromate-treated layer treated with an aqueous solution of chromic anhydride or potassium dichromate, or a chromic acid treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc. Salt treatment layer, etc.

矽烷偶合處理層可使用公知的矽烷偶合劑而形成，也可使用環氧系矽烷、胺基系矽烷、甲基丙烯醯氧基系矽烷、巰基系矽烷、乙烯基系矽烷、咪唑系矽烷、三系矽烷等矽烷偶合劑等而形成。此外，此種矽烷偶合劑也可混合2種以上而使用。其中，較佳為使用胺基系矽烷偶合劑或環氧系矽烷偶合劑而形成的矽烷偶合劑。 The decane coupling treatment layer can be formed using a known decane coupling agent, and epoxy decane, amino decane, methacryloxy decane, decyl decane, vinyl decane, imidazolium decane, and the like can also be used. It is formed by a decane coupling agent, such as a decane. Further, such a decane coupling agent may be used in combination of two or more kinds. Among them, a decane coupling agent formed using an amine decane coupling agent or an epoxy decane coupling agent is preferred.

另外，可對銅箔、表面處理層、耐熱層、防銹層、矽烷偶合處 理層或鉻酸鹽處理層的表面進行例如國際公開編號WO2008/053878、日本特開2008-111169號、日本專利第5024930號、國際公開編號WO2006/028207、日本專利第4828427號、國際公開編號WO2006/134868、日本專利第5046927號、國際公開編號WO2007/105635、日本專利第5180815號、日本特開2013-19056號所記載的表面處理。 In addition, the surface of the copper foil, the surface treatment layer, the heat-resistant layer, the rust-proof layer, the decane coupling treatment layer, or the chromate treatment layer may be, for example, International Publication No. WO 2008/053878, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. 5180815, Japanese Patent Laid-Open No. 2013-19056 The surface treatment described.

[實施例] [Examples]

以下，基於實施例及比較例進行說明。此外，本實施例只不過為一例，並非僅限制於該例。 Hereinafter, description will be made based on examples and comparative examples. Further, the present embodiment is merely an example and is not limited to this example.

<一次粒子層及二次粒子層> <Primary particle layer and secondary particle layer>

首先，熔製具有表1的「銅箔基材的組成」的一欄所記載的組成的鑄錠，將該鑄錠在900℃進行熱軋，獲得厚度10mm的板。然後，反復進行冷軋和退火，最終冷軋至厚度12μm的銅箔，獲得壓延銅箔。另外，作為實施例7的電解銅箔，準備厚度9μm的JX金屬股份有限公司製造的HLP箔。 First, an ingot having the composition described in the column "Composition of a copper foil substrate" in Table 1 was melted, and the ingot was hot rolled at 900 ° C to obtain a plate having a thickness of 10 mm. Then, cold rolling and annealing were repeated, and finally cold rolling was performed to a copper foil having a thickness of 12 μm to obtain a rolled copper foil. Further, as the electrolytic copper foil of Example 7, an HLP foil manufactured by JX Metal Co., Ltd. having a thickness of 9 μm was prepared.

再者，表1的「銅箔基材的組成」一欄的TPC是指韌銅(JIS H3100合金編號C1100)，OFC是指無氧銅(JIS H3100合金編號C1020)。即，例如實施例2的「190ppmAg-TPC」是指在韌銅中添加了190質量ppm的Ag。另外，例如實施例4的「1200ppmSn-OFC」是指在無氧銅中添加了1200質量ppm的Sn。 In addition, TPC of the "composition of copper foil base material" of Table 1 means tough pitch copper (JIS H3100 alloy No. C1100), and OFC means oxygen-free copper (JIS H3100 alloy No. C1020). That is, for example, "190 ppm Ag-TPC" in Example 2 means that 190 mass ppm of Ag is added to the tough pitch copper. Further, for example, "1200 ppm of Sn-OFC" in the fourth embodiment means that 1200 ppm by mass of Sn is added to the oxygen-free copper.

繼而，將該壓延銅箔的表面或該電解銅箔的無光澤面(析出面、M面)側的表面進行電解脫脂、水洗、酸洗後，在表1所示的條件下，在各銅箔基材的該表面形成一次粒子層及/或二次粒子層。表1中記載了「一次粒子層鍍覆電流條件A」及「一次粒子層鍍覆電流條件B」的實施例、比較例是指在A所記載的條件下進行鍍覆後，在B所記載的條件下進一步進行鍍覆。用於形成一次粒子層及二次粒子層的鍍覆液條件示於表1的「一次粒子層鍍覆液A」「一次粒子層鍍覆液B」「二次粒子層鍍覆液」的一欄及以下。例如在「一次粒子層鍍覆液 A」一欄中記載為(1)的情況下，是指使用下述「一次粒子層A形成階段中的鍍覆液條件」的「鍍覆液(1)」形成一次粒子層A。 Then, the surface of the rolled copper foil or the surface on the matte side (precipitated surface, M surface) side of the electrolytic copper foil was subjected to electrolytic degreasing, water washing, and pickling, and then copper was used under the conditions shown in Table 1. This surface of the foil substrate forms a primary particle layer and/or a secondary particle layer. Table 1 shows examples of "primary particle layer plating current condition A" and "primary particle layer plating current condition B", and comparative examples are described in B after plating under the conditions described in A. Further plating is carried out under the conditions. The conditions of the plating solution for forming the primary particle layer and the secondary particle layer are shown in Table 1 "Primary particle layer plating solution A", "primary particle layer plating solution B", and "secondary particle layer plating solution". Column and below. For example, when it is described as (1) in the column of "primary particle layer plating solution A", the following is the "plating solution (1) using the following conditions of the plating solution in the formation stage of the primary particle layer A". The primary particle layer A is formed.

(一次粒子層A形成階段中的鍍覆液條件) (The plating solution condition in the formation stage of the primary particle layer A)

‧鍍覆液(1) ‧ plating solution (1)

液體組成：銅11g/L、硫酸50g/L Liquid composition: copper 11g / L, sulfuric acid 50g / L

液溫：25℃ Liquid temperature: 25 ° C

pH值：1.0~2.0 pH: 1.0~2.0

‧鍍覆液(2) ‧ plating solution (2)

液體組成：銅11g/L、鎢3mg/L、硫酸50g/L Liquid composition: copper 11g / L, tungsten 3mg / L, sulfuric acid 50g / L

液溫：25℃ Liquid temperature: 25 ° C

pH值：1.0~2.0 pH: 1.0~2.0

‧鍍覆液(3) ‧ plating solution (3)

液體組成：銅11g/L、砷100mg/L、硫酸50g/L Liquid composition: copper 11g / L, arsenic 100mg / L, sulfuric acid 50g / L

液溫：25℃ Liquid temperature: 25 ° C

pH值：1.0~2.0 pH: 1.0~2.0

‧鍍覆液(4) ‧ plating solution (4)

液體組成：銅11g/L、鈦6mg/L、硫酸50g/L Liquid composition: copper 11g / L, titanium 6mg / L, sulfuric acid 50g / L

液溫：25℃ Liquid temperature: 25 ° C

pH值：1.0~2.0 pH: 1.0~2.0

‧鍍覆液(5) ‧ plating solution (5)

液體組成：銅11g/L、鉻3mg/L、硫酸50g/L Liquid composition: copper 11g / L, chromium 3mg / L, sulfuric acid 50g / L

液溫：25℃ Liquid temperature: 25 ° C

pH值：1.0~2.0 pH: 1.0~2.0

(一次粒子層B形成階段中的鍍覆液條件) (The plating solution condition in the formation stage of the primary particle layer B)

‧鍍覆液(1) ‧ plating solution (1)

液體組成：銅22g/L、硫酸100g/L Liquid composition: copper 22g / L, sulfuric acid 100g / L

液溫：50℃ Liquid temperature: 50 ° C

pH值：1.0~2.0 pH: 1.0~2.0

(二次粒子層形成階段中的鍍覆條件) (plating conditions in the secondary particle layer formation stage)

‧鍍覆液(1) ‧ plating solution (1)

液體組成：銅15g/L、鎳8g/L、鈷8g/L Liquid composition: copper 15g / L, nickel 8g / L, cobalt 8g / L

液溫：36℃ Liquid temperature: 36 ° C

pH值：2.7 pH: 2.7

‧鍍覆液(2) ‧ plating solution (2)

液體組成：銅15g/L、鎳8g/L、磷1g/L Liquid composition: copper 15g / L, nickel 8g / L, phosphorus 1g / L

液溫：36℃ Liquid temperature: 36 ° C

pH值：2~3 pH: 2~3

‧鍍覆液(3) ‧ plating solution (3)

液體組成：銅15g/L、鎳8g/L、鈷8g/L、鉬8g/L Liquid composition: copper 15g / L, nickel 8g / L, cobalt 8g / L, molybdenum 8g / L

液溫：36℃ Liquid temperature: 36 ° C

pH值：2~3 pH: 2~3

‧鍍覆液(4) ‧ plating solution (4)

液體組成：銅15g/L、鎳8g/L、鎢3g/L Liquid composition: copper 15g / L, nickel 8g / L, tungsten 3g / L

液溫：36℃ Liquid temperature: 36 ° C

pH值：2~3 pH: 2~3

‧鍍覆液(5) ‧ plating solution (5)

液體組成：銅15g/L、鉬8g/L、鈷8g/L Liquid composition: copper 15g / L, molybdenum 8g / L, cobalt 8g / L

液溫：36℃ Liquid temperature: 36 ° C

pH值：2~3 pH: 2~3

<覆蓋鍍覆> <cover plating>

繼而，僅形成有一次粒子層者是在一次粒子層上形成表1所示的覆蓋鍍覆，形成有一次粒子層及二次粒子層者是在二次粒子層上形成表1所示的覆蓋鍍覆。以下記載各自的具體條件。 Then, only the primary particle layer is formed by forming the overcoat plating shown in Table 1 on the primary particle layer, and the primary particle layer and the secondary particle layer are formed to form the coverage shown in Table 1 on the secondary particle layer. Plating. The specific conditions of each are described below.

(1)Ni層 (1) Ni layer

鍍覆液組成：Ni 10g/L Plating solution composition: Ni 10g/L

pH值：2.5 pH: 2.5

溫度：50℃ Temperature: 50 ° C

電流密度Dk：12A/dm² Current density Dk: 12A/dm ²

鍍覆時間：0.5秒 Plating time: 0.5 seconds

鍍覆次數：2次 Number of plating times: 2 times

(2)Ni-Co合金層 (2) Ni-Co alloy layer

鍍浴組成：Ni 10g/L、Co 5g/L Plating bath composition: Ni 10g / L, Co 5g / L

pH值：2.5 pH: 2.5

溫度：50℃ Temperature: 50 ° C

電流密度Dk：10A/dm² Current density Dk: 10A / dm ²

鍍覆時間：0.5秒 Plating time: 0.5 seconds

鍍覆次數：2次 Number of plating times: 2 times

(3)Ni-Zn合金層 (3) Ni-Zn alloy layer

鍍浴組成：Ni 10g/L、Zn 5g/L Plating bath composition: Ni 10g/L, Zn 5g/L

pH值：3.5 pH: 3.5

溫度：40℃ Temperature: 40 ° C

電流密度Dk：2A/dm² Current density Dk: 2A/dm ²

鍍覆時間：1秒 Plating time: 1 second

鍍覆次數：2次 Number of plating times: 2 times

<電解鉻酸鹽處理> <electrolytic chromate treatment>

在形成所述覆蓋鍍覆後，在實施例1~7、比較例2、3中進行以下的電解鉻酸鹽處理。 After the formation of the overcoat plating, the following electrolytic chromate treatments were carried out in Examples 1 to 7 and Comparative Examples 2 and 3.

液體組成：重鉻酸鉀3g/L、Zn 0.5g/L Liquid composition: potassium dichromate 3g / L, Zn 0.5g / L

液溫：40~60℃ Liquid temperature: 40~60°C

pH值：4.0 pH: 4.0

電流密度Dk：2.0A/dm² Current density Dk: 2.0A/dm ²

鍍覆時間：0.6秒 Plating time: 0.6 seconds

鍍覆次數：2次 Number of plating times: 2 times

<矽烷偶合處理> <decane coupling treatment>

在實施例1~7、比較例2、3中進行電解鉻酸鹽處理後，進而進行以下的矽烷偶合處理。 After performing electrolytic chromate treatment in Examples 1 to 7 and Comparative Examples 2 and 3, the following decane coupling treatment was further carried out.

矽烷偶合劑：N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷 Decane coupling agent: N-2-(aminoethyl)-3-aminopropyltrimethoxydecane

矽烷偶合劑濃度：1.0vol% Decane coupling agent concentration: 1.0 vol%

處理溫度：25℃ Processing temperature: 25 ° C

處理時間：3秒 Processing time: 3 seconds

如表1所示，比較例4是代替在所述特定條件下形成一次粒子層及二次粒子層，而將經表面粗化的壓延輥進行調質壓延後的表面於大氣環境下進行熱氧化處理，接著在含有1%CO的氮氣環境下進行加熱還原處理。 As shown in Table 1, in Comparative Example 4, instead of forming the primary particle layer and the secondary particle layer under the specific conditions, the surface of the calendered roll subjected to surface roughening was subjected to thermal oxidation in an atmosphere. The treatment was followed by a heat reduction treatment under a nitrogen atmosphere containing 1% CO.

如表1所示，比較例5是代替在所述特定條件下形成一次粒子層及二次粒子層，而在如下條件下依序實施第1鍍Cu、第2鍍Cu及第3鍍Cu。 As shown in Table 1, in Comparative Example 5, instead of forming the primary particle layer and the secondary particle layer under the specific conditions, the first Cu plating, the second Cu plating, and the third Cu plating were sequentially performed under the following conditions.

(第1鍍Cu條件) (1st Cu plating condition)

鍍浴組成：Cu 150g/L~250g/L、硫酸100g/L Plating bath composition: Cu 150g/L~250g/L, sulfuric acid 100g/L

pH值：1.0 pH: 1.0

溫度：40℃ Temperature: 40 ° C

電流密度Dk：5A/dm² Current density Dk: 5A/dm ²

鍍覆時間：7秒 Plating time: 7 seconds

鍍覆次數：1次 Number of plating times: 1 time

(第2鍍Cu條件) (2nd Cu plating condition)

鍍浴組成：Cu 50g/L~150g/L、硫酸130g/L Plating bath composition: Cu 50g/L~150g/L, sulfuric acid 130g/L

pH值：1.0 pH: 1.0

溫度：25℃ Temperature: 25 ° C

電流密度Dk：40A/dm² Current density Dk: 40A/dm ²

鍍覆時間：7秒 Plating time: 7 seconds

鍍覆次數：1次 Number of plating times: 1 time

(第3鍍Cu條件) (3rd Cu plating condition)

鍍浴組成：Cu 150g/L~250g/L、硫酸100g/L Plating bath composition: Cu 150g/L~250g/L, sulfuric acid 100g/L

pH值：1.0 pH: 1.0

溫度：40℃ Temperature: 40 ° C

電流密度Dk：5A/dm² Current density Dk: 5A/dm ²

鍍覆時間：7秒 Plating time: 7 seconds

鍍覆次數：1次 Number of plating times: 1 time

(十點平均粗糙度Rz的測量) (Measurement of ten point average roughness Rz)

針對各實驗例的表面處理後的銅箔，利用奧林巴斯(Olympus)公司製造的雷射顯微鏡OLS4000測量表面粗糙度Rz。Rz依據JIS B0601 1994。使用物鏡50倍，在銅箔表面的觀察中，在評價長度258μm、臨界值零的條件下，關於壓 延銅箔在與壓延方向垂直的方向(TD)的測量中，或者關於電解銅箔在與電解銅箔的製造裝置中的電解銅箔的行進方向垂直的方向(TD)的測量中，分別變更測量位置而進行10次，求出10次測量的平均值。此外，利用雷射顯微鏡進行的表面粗糙度Rz的測量環境溫度設為23~25℃。關於在兩面設置有表面處理層的銅箔，兩面的十點平均粗糙度Rz均成為相同值。 The surface roughness Rz of the surface-treated copper foil of each experimental example was measured using a laser microscope OLS4000 manufactured by Olympus. Rz is based on JIS B0601 1994. Using the objective lens 50 times, in the observation of the surface of the copper foil, under the condition of evaluating the length of 258 μm and the critical value of zero, the measurement of the direction (TD) of the rolled copper foil in the direction perpendicular to the rolling direction, or regarding the electrolytic copper foil In the measurement of the direction (TD) in which the traveling direction of the electrodeposited copper foil in the manufacturing apparatus of the electrolytic copper foil is perpendicular, the measurement position is changed 10 times, and the average value of 10 measurements is obtained. Further, the measurement ambient temperature of the surface roughness Rz by a laser microscope was set to 23 to 25 °C. Regarding the copper foil provided with the surface treatment layer on both surfaces, the ten-point average roughness Rz of both surfaces has the same value.

(算術平均粗糙度Ra的測量) (Measurement of arithmetic mean roughness Ra)

針對各實驗例的表面處理後的銅箔，利用奧林巴斯公司製造的雷射顯微鏡OLS4000測量表面粗糙度Ra。Ra依據JIS B0601 1994。使用物鏡50倍，在銅箔表面的觀察中，在評價長度258μm、臨界值為零的條件下，關於壓延銅箔在與壓延方向垂直的方向(TD)的測量中，或者關於電解銅箔在與電解銅箔的製造裝置中的電解銅箔的行進方向垂直的方向(TD)的測量中，分別變更測量位置而進行10次，求出10次測量的平均值。此外，利用雷射顯微鏡進行的表面粗糙度Ra的測量環境溫度設為23~25℃。關於在兩面設置有表面處理層的銅箔，兩面的算術平均粗糙度Ra均成為相同值。 The surface roughness Ra of the surface-treated copper foil of each experimental example was measured by a laser microscope OLS4000 manufactured by Olympus. Ra is based on JIS B0601 1994. 50 times of the objective lens, in the observation of the surface of the copper foil, in the measurement of the length of 258 μm and the critical value of zero, the measurement of the rolled copper foil in the direction perpendicular to the rolling direction (TD), or on the electrolytic copper foil In the measurement of the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the manufacturing apparatus of the electrolytic copper foil, the measurement position was changed 10 times, and the average value of the 10 measurements was obtained. Further, the measurement ambient temperature of the surface roughness Ra by a laser microscope was set to 23 to 25 °C. Regarding the copper foil provided with the surface treatment layer on both surfaces, the arithmetic mean roughness Ra of both surfaces becomes the same value.

(Co、Ni及其他元素的附著量的測量) (Measurement of adhesion amount of Co, Ni, and other elements)

Co、Ni及其他元素的附著量是將銅箔樣品的表面處理層在濃度20質量%的硝酸水溶液中溶解，通過ICP發光分析進行測量。在銅箔的兩面設置有表面處理層的實施例、比較例中，在單面貼附耐酸膠帶等掩模，將單面的表面處理層溶解，測量Co、Ni及其他元素的附著量。之後，取下所述掩模，對另一單面測量Co、Ni及其他元素的附著量，或者使用其他樣品測量另一單面的Co、Ni及其他元素的附著量。此外，表1所記載的值設為單面的值。關於在兩面設置有表面處理層的銅箔，兩面的Co、Ni及其他元素的附著量均成為相同值。此外，在Co、Ni及其他元素未溶解於濃度20質量%的硝酸水溶液中的情況下，也可在使用能夠使Co、Ni及其他元素溶解的液體溶解後，通過所述ICP發光分析進行測 量。此外，能夠使Co、Ni及其他元素溶解的液體可使用公知液體、或公知酸性液、或公知鹼性液。 The adhesion amount of Co, Ni, and other elements was obtained by dissolving the surface treatment layer of the copper foil sample in an aqueous solution of nitric acid having a concentration of 20% by mass, and measuring by ICP emission analysis. In the examples and comparative examples in which the surface treatment layer was provided on both surfaces of the copper foil, a mask such as an acid-resistant tape was attached to one surface, and the surface treatment layer of one surface was dissolved, and the adhesion amount of Co, Ni, and other elements was measured. Thereafter, the mask was removed, and the adhesion amount of Co, Ni, and other elements was measured for the other single side, or the adhesion amount of Co, Ni, and other elements of the other single side was measured using another sample. Further, the values described in Table 1 are set to values on one side. Regarding the copper foil provided with the surface treatment layer on both surfaces, the adhesion amounts of Co, Ni, and other elements on both surfaces have the same value. Further, in the case where Co, Ni, and other elements are not dissolved in a 20% by mass aqueous solution of nitric acid, measurement may be performed by the ICP emission analysis after dissolving a liquid capable of dissolving Co, Ni, and other elements. . Further, a known liquid, a known acidic liquid, or a known alkaline liquid can be used as the liquid capable of dissolving Co, Ni, and other elements.

(粒子脫落的評價) (Evaluation of particle shedding)

(1)膠帶測試 (1) Tape test

在表面處理銅箔的經表面處理的一側的表面上貼附透明修補膠帶，將該膠帶沿180°方向剝離時，膠帶因附著於膠帶黏著面的脫落粒子而發生變色，根據所述變色的情況對粉體脫落進行評價。膠帶未變色的情況設為「◎」，變成灰色的情況設為「○」，膠帶變成黑色的情況設為「×」。 A transparent repair tape is attached to the surface of the surface-treated side of the surface-treated copper foil, and when the tape is peeled off in the 180° direction, the tape is discolored due to the detached particles attached to the adhesive surface of the tape, according to the discoloration. The situation was evaluated for powder shedding. When the tape is not discolored, it is set to "◎", when it is gray, it is set to "○", and when the tape is black, it is set to "X".

(2)搬送輥確認 (2) Transfer roller confirmation

在二次電池的製造步驟中，在集電體用銅箔上塗布電極活性物質時使用卷對卷的搬送線。因此，有在搬送線的輥上發生集電體用銅箔表面處理的粗化粒子的脫落的問題。使用用來調整集電體用銅箔的製品寬度的狹縫線裝置，搬送用輥多數情況下每搬送銅箔數千公尺時進行一次清掃，根據該輥污染狀態評價良率。將輥幾乎未受污染的狀態設為「◎」，將略微地看到固著的狀態設為「○」，將輥明顯地被污染的狀態設為「×」。 In the manufacturing process of the secondary battery, a roll-to-roll transfer line is used when the electrode active material is applied onto the copper foil for current collector. Therefore, there is a problem in that the roughened particles which are surface-treated with the copper foil for a current collector are detached on the roller of the conveyance line. In the slit line device for adjusting the width of the product of the copper foil for a current collector, the transfer roller is often cleaned once every time the copper foil is conveyed by several thousand meters, and the yield is evaluated based on the contamination state of the roll. The state in which the roller was almost uncontaminated was set to "◎", the state in which the fixing was slightly observed was "○", and the state in which the roller was significantly contaminated was "x".

(與活性物質的密接性的評價) (Evaluation of adhesion to active material)

與活性物質的密接性是根據以下的順序進行評價。 The adhesion to the active material was evaluated in the following order.

(1)將平均直徑9μm的人工石墨與聚偏二氟乙烯以重量比1：9進行混合，並使其分散至溶劑N-甲基-2-吡咯啶酮中。 (1) Artificial graphite having an average diameter of 9 μm and polyvinylidene fluoride were mixed at a weight ratio of 1:9, and dispersed in a solvent N-methyl-2-pyrrolidone.

(2)在銅箔表面塗布所述活性物質。 (2) Coating the active material on the surface of the copper foil.

(3)將塗布了活性物質的銅箔在乾燥機中進行90℃×30分鐘加熱。此外，此時矽烷偶合劑因為在銅表面未鍵結OH基，所以幾乎未發生利用與未反應的矽烷偶合劑的脫水反應而與銅表面反應的情況。 (3) The copper foil coated with the active material was heated in a dryer at 90 ° C for 30 minutes. Further, at this time, since the decane coupling agent does not bond the OH group to the surface of the copper, the reaction with the copper surface by the dehydration reaction with the unreacted decane coupling agent hardly occurs.

(4)乾燥後，以20mm見方切出，施加1.5噸/mm²×20秒的荷重。 (4) After drying, it was cut out at 20 mm square, and a load of 1.5 ton / mm ² × 20 seconds was applied.

(5)利用切割機將所述樣品以棋盤格狀形成劃痕，貼附市售的黏著膠帶(Sellotape(注冊商標))，放置重量2kg的滾筒使之往返1次而壓接黏著膠帶。 (5) The sample was formed into a checkerboard shape by a cutter, and a commercially available adhesive tape (Sellotape (registered trademark)) was attached, and a roller having a weight of 2 kg was placed and reciprocated once to crimp the adhesive tape.

(6)剝離黏著膠帶，殘存於銅箔上的活性物質將表面的圖像擷取至PC，利用二值化區分銅表面的金屬光澤部分與殘存活性物質的黑色部分，算出活性物質的殘存率。殘存率設為各樣品3個的平均值。活性物質密接性的判定是將殘存率未達50%設為「×」，將50%以上且未達70%設為「△」，將70%以上且未達80%設為「○」，將80%以上且未達90%設為「◎」，將90%以上設為「◎◎」。 (6) The adhesive tape is peeled off, and the active material remaining on the copper foil is taken to the PC, and the metal luster portion of the copper surface and the black portion of the residual material are distinguished by binarization to calculate the residual ratio of the active material. . The residual ratio was set to an average value of three samples. The determination of the adhesiveness of the active material is such that the residual ratio is less than 50% as "X", 50% or more and less than 70% is "△", and 70% or more and less than 80% are set to "○". 80% or more and less than 90% are set to "◎", and 90% or more is set to "◎◎".

(耐熱評價) (heat resistance evaluation)

將表面處理銅箔切割為20cm×20cm尺寸的大小後，向加熱至300℃的烘箱中投入銅箔切割樣品，經過15秒後將銅箔樣品從烘箱取出，評價表面處理的氧化變色程度。將完全未發生氧化變色的銅箔設為「○」，將未達20cm×20cm尺寸的3成發黑地產生氧化變色的銅箔設為「△」，將3成以上發黑地產生氧化變色的銅箔設為「×」。 After the surface-treated copper foil was cut into a size of 20 cm × 20 cm, the copper foil was cut into an oven heated to 300 ° C, and after 15 seconds, the copper foil sample was taken out from the oven, and the degree of oxidative discoloration of the surface treatment was evaluated. The copper foil which does not cause oxidative discoloration at all is set to "○", and the oxidized discoloration of the copper foil which is less than 20 cm × 20 cm in size is set to "△", and oxidative discoloration occurs in 30% or more of black. The copper foil is set to "X".

(評價結果) (Evaluation results)

實施例1~14的粒子脫落評價均良好，與活性物質的密接性良好，耐熱性也良好。 The particles of Examples 1 to 14 were all evaluated to have good adhesion, and the adhesion to the active material was good, and the heat resistance was also good.

比較例1因為未設置二次粒子層，所以十點平均粗糙度Rz及算術平均粗糙度Ra偏離特定的範圍，因此粒子脫落評價、密接性均不良。另外，因為未形成二次粒子層，且也未設置覆蓋鍍覆，所以耐熱性也不良。 In Comparative Example 1, since the secondary particle layer was not provided, the ten-point average roughness Rz and the arithmetic mean roughness Ra deviated from a specific range, and thus the particle fall-off evaluation and the adhesion were poor. Further, since the secondary particle layer is not formed and the coating plating is not provided, the heat resistance is also poor.

比較例2因為未設置一次粒子層，所以十點平均粗糙度Rz偏離特定的範圍，因此粒子脫落評價、密接性均不良。 In Comparative Example 2, since the primary particle layer was not provided, the ten-point average roughness Rz deviated from the specific range, and thus the particle fall-off evaluation and the adhesion were poor.

比較例3雖然設置了一次粒子層及二次粒子層，但十點平均粗糙度Rz及算術平均粗糙度Ra偏離特定的範圍，因此密接性的評價限於「△」。 In Comparative Example 3, since the primary particle layer and the secondary particle layer were provided, the ten point average roughness Rz and the arithmetic mean roughness Ra deviated from the specific range, and therefore the evaluation of the adhesion was limited to "Δ".

比較例4雖然十點平均粗糙度Rz為特定範圍內，但僅壓延處理無法依序形成一次粒子層及二次粒子層，因此密接性不充分。另外，因為也未設置覆蓋鍍覆層，所以耐熱性能不良。 In Comparative Example 4, although the ten-point average roughness Rz was within a specific range, the primary particle layer and the secondary particle layer could not be sequentially formed by the rolling treatment, and thus the adhesion was insufficient. Further, since the coating plating layer is not provided, the heat resistance is poor.

比較例5雖然十點平均粗糙度Rz為特定範圍內，但在所述鍍覆條件下無法依序形成一次粒子層及二次粒子層，因此粒子脫落測試的結果欠佳，密接性不充分。 In Comparative Example 5, although the ten-point average roughness Rz was within a specific range, the primary particle layer and the secondary particle layer could not be sequentially formed under the plating conditions. Therefore, the result of the particle fall-off test was poor, and the adhesion was insufficient.

Claims (27)

一種電池用表面處理銅箔，其具有：銅箔；及位於該銅箔的至少一表面側的表面處理層；該表面處理層具有一次粒子層、二次粒子層，且依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對該表面處理層表面進行測量時的十點平均粗糙度Rz為1.8μm以上。  A surface-treated copper foil for a battery, comprising: a copper foil; and a surface treatment layer on at least one surface side of the copper foil; the surface treatment layer having a primary particle layer and a secondary particle layer, and used according to JIS B0601 1994 The ten-point average roughness Rz when the surface of the surface-treated layer was measured by a laser microscope having a wavelength of 405 nm was 1.8 μm or more.   如申請專利範圍第1項之電池用表面處理銅箔，其中，依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對該表面處理層表面進行測量時的算術平均粗糙度Ra為0.26μm以上。  The surface-treated copper foil for a battery according to the first aspect of the invention, wherein the arithmetic mean roughness Ra when the surface of the surface-treated layer is measured using a laser microscope having a wavelength of 405 nm is 0.26 μm or more in accordance with JIS B0601 1994.   如申請專利範圍第1項之電池用表面處理銅箔，其中，該一次粒子層含有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。  The surface treated copper foil for a battery according to claim 1, wherein the primary particle layer contains a layer selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. More than one in the group.   如申請專利範圍第2項之電池用表面處理銅箔，其中，該一次粒子層含有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。  The surface treated copper foil for a battery according to claim 2, wherein the primary particle layer contains a layer selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. More than one in the group.   如申請專利範圍第1項之電池用表面處理銅箔，其中，該二次粒子層含有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。  The surface treated copper foil for a battery according to claim 1, wherein the secondary particle layer contains a layer selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. More than one in the group.   如申請專利範圍第2項之電池用表面處理銅箔，其中，該二次粒子層含有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。  The surface treated copper foil for a battery according to the second aspect of the invention, wherein the secondary particle layer is selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. More than one in the group.   如申請專利範圍第3項之電池用表面處理銅箔，其中，該二次粒子層含有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的 群中的一種以上。  The surface treated copper foil for a battery according to claim 3, wherein the secondary particle layer comprises a layer selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. More than one in the group.   如申請專利範圍第4項之電池用表面處理銅箔，其中，該二次粒子層含有選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。  The surface treated copper foil for a battery according to claim 4, wherein the secondary particle layer contains a layer selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, P, and Sn. More than one in the group.   如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該表面處理層含有合計100μg/dm ²以上的選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。 The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the surface treatment layer contains a total of 100 μg/dm ² or more selected from the group consisting of Cu, W, Ti, As, V, Mo, and Ni. One or more of the groups consisting of Co, Cr, Zn, P, and Sn. 如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該表面處理層含有合計10000μg/dm ²以下的選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上。 The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the surface treatment layer contains a total of 10000 μg/dm ² or less selected from the group consisting of Cu, W, Ti, As, V, Mo, and Ni. One or more of the groups consisting of Co, Cr, Zn, P, and Sn. 如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該表面處理層含有Ni，且Ni的附著量為100μg/dm ²以上。 The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the surface treatment layer contains Ni, and the adhesion amount of Ni is 100 μg/dm ² or more. 如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該表面處理層含有Ni，且Ni的附著量為4500μg/dm ²以下。 The patent in any one of the range of the battery 1 to 8 surface treated copper foil, wherein the surface treatment layer containing Ni, and Ni deposition amount of 4500μg / dm ² or less. 如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該表面處理層含有Co，且Co的附著量為100μg/dm ²以上。 The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the surface treatment layer contains Co, and the adhesion amount of Co is 100 μg/dm ² or more. 如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該表面處理層含有Co，且Co的附著量為6000μg/dm ²以下。 The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the surface treatment layer contains Co, and the adhesion amount of Co is 6000 μg/dm ² or less. 如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該一次粒子層由Cu構成。  The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the primary particle layer is made of Cu.   如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該二次粒子層由Cu、Co、Ni構成。  The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the secondary particle layer is composed of Cu, Co, and Ni.   如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其滿足以下的(17-1)~(17-8)的任一個或兩個或三個或四個或五個或六個或 七個或八個：(17-1)該表面處理層含有合計100μg/dm ²以上的選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上；(17-2)該表面處理層含有合計10000μg/dm ²以下的選自由Cu、W、Ti、As、V、Mo、Ni、Co、Cr、Zn、P及Sn所組成的群中的一種以上；(17-3)該表面處理層含有Ni，且Ni的附著量為100μg/dm ²以上；(17-4)該表面處理層含有Ni，且Ni的附著量為4500μg/dm ²以下；(17-5)該表面處理層含有Co，且Co的附著量為100μg/dm ²以上；(17-6)該表面處理層含有Co，且Co的附著量為6000μg/dm ²以下；(17-7)該一次粒子層由Cu構成；(17-8)該二次粒子層由Cu、Co、Ni構成。 The surface-treated copper foil for a battery according to any one of claims 1 to 8, which satisfies any one or two or three or four or five of the following (17-1) to (17-8) Or six or seven or eight: (17-1) the surface treatment layer contains a total of 100 μg / dm ² or more selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, Zn, One or more of the groups consisting of P and Sn; (17-2) the surface treatment layer containing a total of 10000 μg/dm ² or less selected from the group consisting of Cu, W, Ti, As, V, Mo, Ni, Co, Cr, and Zn And (17-3) the surface treatment layer contains Ni, and the adhesion amount of Ni is 100 μg/dm ² or more; (17-4) the surface treatment layer contains Ni, and The adhesion amount of Ni is 4500 μg/dm ² or less; (17-5) the surface treatment layer contains Co, and the adhesion amount of Co is 100 μg/dm ² or more; (17-6) the surface treatment layer contains Co, and Co The adhesion amount is 6000 μg/dm ² or less; (17-7) the primary particle layer is composed of Cu; and (17-8) the secondary particle layer is composed of Cu, Co, and Ni. 如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其滿足以下的(18-1)及(18-2)中的任一個或兩個：(18-1)依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對該表面處理層表面進行測量時的十點平均粗糙度Rz滿足以下的(18-1-1)及(18-1-2)中的任一個或兩個：(18-1-1)依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對該表面處理層表面進行測量時的十點平均粗糙度Rz滿足以下的任一個：‧為1.9μm以上，‧為2.0μm以上，‧為2.1μm以上，(18-1-2)依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對該表面處理層表面進行測量時的十點平均粗糙度Rz滿足以下的任一個：‧為10μm以下， ‧為8μm以下，‧為5μm以下，‧為3.30μm以下，‧為3.20μm以下，‧為3.10μm以下，‧為3.05μm以下，‧為2.85μm以下；(18-2)依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對該表面處理層表面進行測量時的算術平均粗糙度Ra滿足以下的(18-2-1)及(18-2-2)中的任一個或兩個：(18-2-1)依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對該表面處理層表面進行測量時的算術平均粗糙度Ra滿足以下的任一個：‧為0.28μm以上，‧為0.30μm以上，‧為0.32μm以上，(18-2-2)依據JIS B0601 1994，使用波長405nm的雷射顯微鏡對該表面處理層表面進行測量時的算術平均粗糙度Ra滿足以下的任一個：‧為5.0μm以下，‧為4.5μm以下，‧為4.0μm以下，‧為3.5μm以下，‧為3.0μm以下，‧為2.5μm以下，‧為2.0μm以下， ‧為1.5μm以下，‧為1.0μm以下，‧為0.45μm以下，‧為0.44μm以下，‧為0.41μm以下，‧為0.40μm以下。  The surface-treated copper foil for a battery according to any one of claims 1 to 8, which satisfies one or both of the following (18-1) and (18-2): (18-1) JIS B0601 1994, the ten-point average roughness Rz when the surface of the surface treatment layer is measured using a laser microscope having a wavelength of 405 nm satisfies any of the following (18-1-1) and (18-1-2) or Two: (18-1-1) According to JIS B0601 1994, the ten-point average roughness Rz when the surface of the surface treatment layer is measured using a laser microscope having a wavelength of 405 nm satisfies any of the following: ‧ is 1.9 μm or more, ‧ is 2.0 μm or more, ‧ is 2.1 μm or more, and (18-1-2) according to JIS B0601 1994, the ten-point average roughness Rz when the surface of the surface treatment layer is measured using a laser microscope having a wavelength of 405 nm satisfies the following Any one: ‧ is 10 μm or less, ‧ is 8 μm or less, ‧ is 5 μm or less, ‧ is 3.30 μm or less, ‧ is 3.20 μm or less, ‧ is 3.10 μm or less, ‧ is 3.05 μm or less, and ‧ is 2.85 μm or less; -2) Arithmetic when measuring the surface of the surface treated layer using a laser microscope with a wavelength of 405 nm according to JIS B0601 1994 The average roughness Ra satisfies either or both of (18-2-1) and (18-2-2): (18-2-1) according to JIS B0601 1994, using a laser microscope with a wavelength of 405 nm The arithmetic mean roughness Ra when the surface of the surface treatment layer is measured satisfies any of the following: ‧ is 0.28 μm or more, ‧ is 0.30 μm or more, ‧ is 0.32 μm or more, and (18-2-2) is based on JIS B0601 1994 The arithmetic mean roughness Ra when the surface of the surface treatment layer was measured using a laser microscope having a wavelength of 405 nm satisfies any of the following: ‧ is 5.0 μm or less, ‧ is 4.5 μm or less, ‧ is 4.0 μm or less, and ‧ is 3.5 μm Hereinafter, ‧ is 3.0 μm or less, ‧ is 2.5 μm or less, ‧ is 2.0 μm or less, ‧ is 1.5 μm or less, ‧ is 1.0 μm or less, ‧ is 0.45 μm or less, ‧ is 0.44 μm or less, and ‧ is 0.41 μm or less. ‧ is 0.40 μm or less.   如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該銅箔含有合計5質量ppm以上且0.3質量%以下的選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及Mg所組成的群中的一種以上。  The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the copper foil contains a total of 5 mass ppm or more and 0.3 mass% or less selected from the group consisting of In, Au, Pd, Ag, Cr, One or more of the group consisting of Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B, and Mg.   如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該銅箔含有合計5質量ppm以上且300質量ppm以下的選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及Mg所組成的群中的一種以上。  The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the copper foil contains a total of 5 mass ppm or more and 300 mass ppm or less selected from the group consisting of In, Au, Pd, Ag, Cr, One or more of the group consisting of Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B, and Mg.   如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該銅箔含有合計301質量ppm以上且0.3質量%以下的選自由In、Au、Pd、Ag、Cr、Fe、P、Ti、Sn、Zn、Mn、Mo、Co、Ni、Si、Zr、B及Mg所組成的群中的一種以上。  The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the copper foil contains 301 mass ppm or more and 0.3 mass% or less in total selected from the group consisting of In, Au, Pd, Ag, Cr, One or more of the group consisting of Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Zr, B, and Mg.   如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其中，該表面處理層在該二次粒子層上進而具有選自由耐熱層、防銹層、鉻酸鹽處理層、矽烷偶合處理層、鍍覆層、樹脂層所組成的群中的1種以上的層。  The surface-treated copper foil for a battery according to any one of claims 1 to 8, wherein the surface treatment layer further has a heat-resistant layer, a rust-proof layer, and a chromate-treated layer on the secondary particle layer. One or more layers of the group consisting of a decane coupling treatment layer, a plating layer, and a resin layer.   如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其為二次電池用。  The surface-treated copper foil for a battery according to any one of claims 1 to 8, which is for a secondary battery.   如申請專利範圍第1至8項中任一項之電池用表面處理銅箔，其 為二次電池集電體用。  The surface-treated copper foil for a battery according to any one of claims 1 to 8, which is for a secondary battery current collector.   一種集電體，其具有申請專利範圍第1至24項中任一項之電池用表面處理銅箔。  A current collector having a surface-treated copper foil for a battery according to any one of claims 1 to 24.   一種電極，其具有申請專利範圍第1至24項中任一項之電池用表面處理銅箔。  An electrode having a surface-treated copper foil for a battery according to any one of claims 1 to 24.   一種電池，其具有申請專利範圍第1至24項中任一項之電池用表面處理銅箔或申請專利範圍第19項之集電體或申請專利範圍第20項之電極。  A battery comprising the surface-treated copper foil for a battery according to any one of claims 1 to 24, or the current collector of claim 19 or the electrode of claim 20 of the patent application.