201205931 六、發明說明： 【發明所屬之技術領織】 本發明係關於-種鐘離子電池集電器用㈣，尤 於-種經離子二次電池負極集電器用銅箱。 、 【先前技術】 鋰離子電池具有能量密户古 ^ ^ X阿、可獲得較高之電壓之特 徵，多用於筆記型電腦、攝影機 寻 小型電子機器。認為將來亦有希望用作電動汽車或並通ί 庭之分散配置型電源此類大型機器之電源。 / a豕 貍離子電池之電極體通常具有正極、隔板及負極捲繞 或積層幾十層之堆疊構造。通堂 通吊’正極係由鋁箱所製成之 ” ι與设置於其表面之LiCQ〇2、UNi〇2及㈣〜〇4 j經複合氧化物作為材料之正極活性物質所構成，負極係 以銅泊所構成之負極集電器與塗佈於其表面之碳等作為 材料之負極活性物質所構成。 用作負極集電器之銅落之重要課題有其與負極活性物 μ之密合性，先前以提昇該密合性為中心而對集電器用銅 泊進行研究開發。用以改善與活性物質之密合性之一般方 可舉稱為事先粗化處理之於㈣表面形成凹凸的表面 处理。粗化處理之方法，已知有喷砂處理、藉由粗面輥所 進行之壓延、機械研磨、電解研磨、化學研磨及電沉積粒 子：鍍敷等方法’該等之中’肖別以電沉積粒子之鍍敷最 為常用°亥技街，係為了下述目的而進行··使用硫酸銅酸 敷/谷於銅油表面將銅電沉積為多數之樹枝狀或小球 201205931 狀，形成微細之凹凸，藉定準效應謀求密合性的改善，或 於體積變化大之活性物質膨脹時，使應力集中於活性物質 層的凹部而形成龜裂’肖止因應力集中於集電器界面所導 致之剝離（例如，日本特許第3733〇67號公報）。 於日本專利第3733G65號公報中，揭示有以粗链度之 參數來具體界定較佳之表面性狀，並藉由將表面㈣度^ 之值大之銅猪用作為集電器’提昇集電器與活性物質之密 合性（㈣G209)。集電器之表面㈣度Ra較佳為〇〇1" m以上，更佳為0.01〜u m，進而更佳為〇 〇5〜〇 $以爪（段 落〇〇21 #)。帛電器之表面粗糙度Ra肖局部頂端之平均間 隔S較佳為具有i00Rags之關係（段落〇〇22等）。集電器 表面之凹凸之凸部的形狀較佳為錐體狀（段落〇〇23等）。° 並且揭示有該類表面形態可以於電解銅箔（段落 〇〇44)、藉由電解法使銅析出於壓延銅③之表面而將表面粗 化（段落0045 )，及以砂紙進行研磨處理（段落〇2〇5)而 獲得。 [專利文獻1]曰本專利第3733067號公報 [專利文獻2]日本專利第3733〇65號公報 【發明内容】 鐘離子電池之電池電容根據負極活性物質之塗佈量而 發生變化’因此為實現電池特性之穩定化，負極活性物質 之塗佈量之控制/管理變得重要，但現狀為負㈣性物質 之塗佈步驟中之塗佈量之管理係根據包含塗佈後之鋼羯之 重量而進行。目此，若不固定作為集電器之銅落之厚度則 201205931 無法適當管理應塗佈之負極活性物質之量。銅猪之比重約 為8.92g/cm3,料負極活性物質之碳之比重約為 ⑽3,故而例如相當於銅落之厚度〇.1“ m的碳之厚度為h78 β m因此’於以厚纟j 〇 " m為目標製造銅箔時厚度僅 〇.1" m ( 1.〇〇〇/0)之不均，會使碳之厚度產生高達口 (於以厚度40”為目標之情形時相當於4 45%)之誤差。 其於40// m厚度之活性物質中，相當於4 45%之不均。即 結果為mi之微小厚度^均㈣㈣物f之厚度造成較 大影響。因此期望板厚精度優異之銅箔。 然而’集電器用銅羯之迄今為止之開發之方向，壓倒 性的為表面性狀控制’其係提昇與負極活性物質之密合性 為目的之微觀觀點。因&，以宏觀觀點提昇銅落之板厚精 度而實現鋰離子電池之電容穩定性之課題仍未解決。 因此’本發明之録題之一在於提供—種板厚精度高之 鋰離子電池集電器用銅箔。χ，本發明之其他課題之一在 於提供該種銅箔之製造方法。 銅羯大致分為壓延銅箱及電解銅荡。於壓延銅猪中， 板厚精度多取決於魔延機之功能（能力），而對於現狀之壓 延機’於以板厚精度為目標之板厚心m中±16%為其限 度。根本性對策亦期望壓延機之改造或開發，但需要高額 之研究開發費用’因此難以立刻進行。 本發明人在上述情況下’為解決上述課題而反覆研 究，結果於壓延銅结之製造過程中’壓延大多為前饋的板 厚控制’因此關於製品之板厚精度’最終冷軋之最終道次 201205931 (find pass)前的表面㈣度之不均 之因素之-，著眼於上述情況厚控制&成影響 . 現於最終道次之前階段 中減小表面粗縫度’並減小表面粗輪度之不均， ： 板厚精度。具體而言，明白藉由於 . 取、，、遏-人刖之壓延中佶 用表面粗縫度小之工作輥’於最終道次中使用所需之表^ 粗縫度之工作報，最終可獲得板厚精度良好、具有所需之 表面粗糙度之銅箔。就考慮與活 ^ . 丨物質之密合性之關係而 吕，於集電器用銅箔中要求特定 心衣囟粗糙度，但藉由於 最科軋之最終道次前龍儘可能減小表面粗㈣，可於 提尚板厚精度的同時具有所需之表面粗糙度。 以上述認識為基^完成之本發明於—離樣中，為一 種經離子電池集電器用㈣，其係壓延平行方向之表面粗 縫度Ra之平均值（Raavg)為〇.〇1〜〇15//m ARa avamax —Ramin 為 〇·〇25 y m 以下。 於本發明之鋰離子電池集電器用銅落之一實施形態 中’銅箔之板厚為5〜20 a m。 於本發明之鋰離+電池集電器用mi之另一實施形態 中’銅落之板厚之最大值（tmax)與板厚之平均值（tavg)之 差’或最小值（tmin)與板厚之平均值（tavg)之差中之任意 較大值對於板厚之平均值（tavg)之比例為13%以下。 於本發明之鋰離子電池集電器用銅落之一實施形態 中ARSm RSmmax—RSmmin對於壓延平行方向之表面粗輪 度 RSm 之平均值（RSmavg)之比（ARSm/RSm“g)為 〇 5 201205931 ▲於本發明之鐘離子電池集電器用銅猪之其他-實施形 態中’銅治為鋰離子二次電池負極集電器用。 本發明於其他一態檨φ氣 集電器之鐘離子電池。一種-備本發明之銅落作為 本發明進而於其他-態樣_，為一種鐘離子電 器用銅箔之製造方法，直係 集電 β A 、係於最終冷軋步驟中，用於最& 道次之工作親之表面粗輪度R…·。3…上，用於= 道次前之1道次之工作輥 、最終 本發明之銅箱係板=:ΓΓ未達一。 :生物質之塗佈量之誤差，從而可實 == 電池電容之穩定化。 $離千電池之 【實施方式】 於本發明甲使用之銅 包含銅合金落。㈣之材:=，。「㈣」中亦 途或要求特性進行適當選擇即了無特別限制，只要根據用 除高純度之銅（，氧例如’雖然無限定，但 〜，、^^丁…把广之外’亦可列舉添加有 -…銅合金， 以系銅合金之類之鋼合 4之Cu-心系、Cu — 對連續發生振動之環境 強度高、可應 銅_並無特別限制，！=面優異。 當選擇即可。通常為、要根據要求特性進行適 極之集電器之情形時，使銅Π:變用^ m，更典型為5 201205931 〜20 // m左右。 本發明之銅箔係根據壓延平 主疋十仃方向之表面粗糙度Ra之 平均值（Raavg)，及 ARa。Ra ~~ I? max~ Ramin而規定。Ra為將粗 I度曲線自中心線對折，將該_度曲線及中心線所得之 面積除以基準長度L而得之值，依據咖讓：纖而測 :。於本發明中所謂表面粗縫度^之平均值…。為任 J0點之平均值’於本發明中所謂仏係所測定之1〇點 之以中，作為最大值之Ramax與作為最小值之^之差。 其中’此處所謂任意之1G點’並非指各敎點相互處於附 近之ίο,點，例#若於線圈狀之情形時，則根據所得長度， 以於壓延方向至少為150mm間隔、較佳為4〇〇mm間隔更 佳為ImM隔以上選擇10 .點。各測定點中係由對測定 點附近測$ 3二欠之平均值而。再纟，各測定點係選取寬 度方向中央之Ra。又，於將電池分解之情形時，即便為重 疊有複數個之負極用銅箔之薄片若亦可確保1 5〇mm以上之 測定間隔’則可對該薄片測定表面粗糙度。 本發明之銅箔之特徵在於：關於壓延平行方向之表面 粗糙度Ra之平均值（Raavg)滿足〇 〇1〜〇 15//m。以〇 〇1 emSRa$0.15/zm作為條件之原因在於：若Ra未達〇〇1 以m則表面平滑而無法獲得與負極活性物質之充分之密合 性，另一方面，若超過〇. 15 v m，則即便藉由最終道次前之 壓延而減小粗糙度，使表面粗糖度成為不均較少之狀態， 亦會因最終道次之壓延而導致不均。然而，若考慮穩定製 成表面傷痕等表面缺陷少之外觀品質之觀點，則期望Ra為201205931 VI. Description of the Invention: [Technical woven fabric according to the invention] The present invention relates to a fourth type of ion battery collector (IV), and more particularly to a copper box for an ion secondary battery negative electrode collector. [Prior Art] Lithium-ion batteries have the characteristics of high voltage, which can be used for notebook computers and cameras to find small electronic machines. It is believed that there will be a future power source for large machines such as electric vehicles or distributed power supplies. The electrode body of the arsenic ion battery usually has a stacked structure in which a positive electrode, a separator, and a negative electrode are wound or laminated in several layers. Tongtangtong's 'positive electrode is made of aluminum box" and ι is composed of LiCQ〇2, UNi〇2 and (4)~〇4j disposed on the surface of the composite active material as a material. It is composed of a negative electrode current collector composed of a copper plate and a negative electrode active material which is coated with carbon or the like as a material. The important problem of the copper drop used as a negative electrode current collector is that it is in close contact with the negative electrode active material μ. In the past, research and development of copper ferrules for current collectors have been carried out centering on the improvement of adhesion. The general method for improving the adhesion to active materials can be referred to as pre-roughening treatment (4) surface treatment for forming irregularities on the surface. For the roughening treatment, there are known sandblasting treatment, calendering by rough roll, mechanical grinding, electrolytic grinding, chemical grinding, and electrodeposition of particles: plating, etc. The plating of electrodeposited particles is most commonly used in Haiji Street, which is carried out for the following purposes: • The use of copper sulphate/valley on the surface of copper oil to electrodeposite copper into a plurality of dendritic or globules 201205931, forming fine Bump, borrow The quasi-effect seeks to improve the adhesion, or when the active material that has a large volume change expands, the stress is concentrated on the concave portion of the active material layer to form a crack, which is caused by stress concentration at the collector interface (for example, Japanese Patent No. 3733〇67. In Japanese Patent No. 3733G65, it is disclosed that the preferred surface properties are specifically defined by the parameters of the thick chain, and the copper pigs having a large surface (four) degree are used. As a current collector, the adhesion between the current collector and the active material is improved ((4) G209). The surface (four) degree Ra of the current collector is preferably 〇〇1 " m or more, more preferably 0.01~um, and even more preferably 〇〇5~ 〇$以 claw (paragraph 〇〇21#). The average interval S of the top surface of the surface roughness Ra of the electric appliance is preferably a relationship of i00Rags (paragraph 〇〇22, etc.). The convex portion of the surface of the current collector The shape is preferably a cone shape (paragraph 〇〇 23, etc.) ° and reveals that such surface morphology can be deposited on the surface of the rolled copper 3 by electrolytic copper foil (paragraph 〇〇 44) by electrolysis. Surface roughening (paragraph 0045 And the grinding treatment by the sandpaper (paragraph 〇2〇5). [Patent Document 1] Japanese Patent No. 3733067 [Patent Document 2] Japanese Patent No. 3733〇65 [Invention] The battery capacity varies depending on the amount of application of the negative electrode active material. Therefore, in order to stabilize the battery characteristics, the control/management of the coating amount of the negative electrode active material becomes important, but the current application step of the negative (tetra) substance The management of the coating amount is carried out according to the weight of the steel ruthenium after coating. Therefore, if the thickness of the copper slab as the current collector is not fixed, 201205931 cannot properly manage the amount of the negative electrode active material to be applied. The specific gravity of the copper pig is about 8.92 g/cm3, and the carbon of the negative electrode active material has a specific gravity of about (10)3, so that, for example, the thickness of the copper drop is 〇.1" m, the thickness of the carbon is h78 β m, so the thickness is 纟j 〇" m is the target when manufacturing copper foil, the thickness is only 〇.1" m ( 1.〇〇〇/0) unevenness, which will cause the thickness of carbon to be as high as the mouth (in the case of thickness 40) Equivalent to 4 45%) error. It is equivalent to 4 45% unevenness in the active material of thickness 40/m. That is, the result is a small thickness of mi ^ (4) (four) the thickness of the object f causes a greater influence. Therefore, a copper foil excellent in sheet thickness precision is desired. However, the development direction of the copper enamel for collectors has been overwhelmingly controlled by the surface properties, which is a microscopic viewpoint for improving the adhesion to the negative electrode active material. The problem of achieving the capacitance stability of lithium-ion batteries by raising the thickness of the copper in a macroscopic view is still unresolved. Therefore, one of the problems of the present invention is to provide a copper foil for a lithium ion battery current collector having a high plate thickness precision. One of the other problems of the present invention is to provide a method for producing such a copper foil. The copper plaque is roughly divided into a rolled copper box and an electrolytic copper slab. In the rolled copper pig, the accuracy of the plate thickness depends on the function (capacity) of the magic extension machine, and the current calender is limited to ±16% of the plate thickness m of the plate thickness precision. Fundamental countermeasures also require the modification or development of the calender, but it requires a high amount of research and development costs, so it is difficult to carry out immediately. In the above case, the inventors have repeatedly studied in order to solve the above problems, and as a result, in the manufacturing process of the rolled copper junction, the rolling is mostly the feed-through thickness control. Therefore, regarding the plate thickness accuracy of the product, the final cold rolling is finalized. Sub-201205931 (find pass) before the surface (four) degree of unevenness - focus on the above situation thick control & into the effect. Now reduce the surface roughness in the final stage of the final pass 'reduce the surface roughness Uneven rotation, thickness accuracy. Specifically, it is understood that by using, taking, and suppressing, the work roll of the surface roll with a small surface roughness is used in the final pass, and the work report of the rough seam is finally obtained. A copper foil having a good plate thickness accuracy and having a desired surface roughness is obtained. Considering the relationship between the adhesion of the material and the material, the specific heart-coating roughness is required in the copper foil for collectors, but the surface roughness is reduced as much as possible by the final pass of the most suitable rolling. (4) It can provide the required surface roughness while improving the thickness accuracy. Based on the above knowledge, the present invention is completed in an isolated ion battery (IV), and the average value (Raavg) of the surface roughness Ra in the direction parallel to the rolling is 〇.〇1~〇 15//m ARa avamax —Ramin is 〇·〇25 ym or less. In one embodiment of the copper drop for a lithium ion battery current collector of the present invention, the thickness of the copper foil is 5 to 20 m. In another embodiment of the lithium ion-free battery current collector of the present invention, the difference between the maximum value (tmax) of the plate thickness of the copper drop and the average value (tvg) of the plate thickness (tmin) and the plate The ratio of any larger value of the difference in the average value of the thickness (tavg) to the average value of the sheet thickness (tavg) is 13% or less. In the embodiment of the copper drop for the lithium ion battery current collector of the present invention, the ratio of the average value (RSmavg) of the surface rough wheel RSm (ARSm/RSm "g) of the surface roughness RD of the rolling parallel direction is 〇5 201205931 ▲In other embodiments of the copper pig for the ion battery collector of the present invention, the 'copper rule is used for the lithium ion secondary battery anode current collector. The clock ion battery of the invention is the other one. - The copper drop of the present invention is further described in the present invention as a method for producing a copper foil for a clock ion electric appliance, and the direct current collection β A is used in the final cold rolling step for the most & The working order of the pass is on the surface coarse rotation R...·3..., for the work roll of the first pass of the pass, and finally the copper box of the present invention =: ΓΓ does not reach one. : biomass The error of the coating amount can be stabilized == Stabilization of the battery capacity. [Embodiment] The copper used in the invention of the present invention comprises a copper alloy. (4) The material: =, "(4)" There is no special restriction on the way or the required characteristics to be properly selected, as long as the root In addition to high-purity copper (oxygen, for example, 'not limited, but ~, ^ ^ butyl ... can be widely used to add - ... copper alloy, to copper alloy and the like 4 -Heart system, Cu - High ambient strength for continuous vibration, copper can be used without special restrictions, and the surface is excellent. When selecting, it is usually necessary to carry out the appropriate collector according to the required characteristics. To make the copper Π: use ^ m, more typically 5 201205931 ~ 20 / m. The copper foil of the present invention is based on the average of the surface roughness Ra of the rolling flat main 疋 direction (Raavg), and ARa Ra ~~ I? max~ Ramin is specified. Ra is the value obtained by dividing the rough I degree curve from the center line, dividing the area obtained by the _ degree curve and the center line by the reference length L, according to the coffee: fiber Further, in the present invention, the average value of the surface roughness degree ^ is the average value of any J0 point 'in the first point measured by the so-called lanthanide system in the present invention, and Ramax is the maximum value. As the difference between the minimum values, where 'the so-called arbitrary 1G point' does not mean that the defects are in the vicinity of each other. Ίο,点,例# In the case of a coil shape, according to the obtained length, at least 150 mm intervals in the rolling direction, preferably 4 mm interval, more preferably 1 mM interval or more. In the middle, the average value of $3 is measured in the vicinity of the measurement point. Further, each measurement point is Ra in the center in the width direction. Further, in the case of decomposing the battery, even if a plurality of negative electrodes are overlapped The sheet of copper foil can also be used to measure the surface roughness of the sheet if it can ensure a measurement interval of 15 mm or more. The copper foil of the present invention is characterized by an average value of the surface roughness Ra in the direction parallel to the calendering (Raavg ) Meet 〇〇1~〇15//m. The reason why 〇〇1 emSRa$0.15/zm is used as a condition is that if Ra is less than 〇〇1, the surface is smooth and sufficient adhesion to the negative electrode active material cannot be obtained, and if it exceeds 〇. 15 vm Even if the roughness is reduced by the rolling before the final pass, the surface roughness is made less uneven, and unevenness is caused by the final pass. However, considering the viewpoint of stabilizing the appearance quality such as surface defects such as surface flaws, it is desirable that Ra is
S 8 201205931 0.03"m以上’更佳之範圍為〇 〇3"msRas〇 又’其特徵亦在於：滿足Ramn為〇 〇25 ^ 、下以ARa — — Ramjn為0.025 v m作為條件之 原因在於：若作為製品之最終壓延後之銅箔的為〇 〇25 "01以下’則意味著最終壓延之最終道次前之ARa為0.025 # m以下。若最終壓延之最終道次前之ARa為〇 〇25 "爪以 下，則於最終壓延之最終道次時因表面粗糙度之不均（變 動）而對板厚控制之影響較小，即最終道次中之製品之板 厚精度提昇。於ARa超過0.025 // m之情形時，最終壓延之 最終道次前之ARa超過〇·〇25 " m之情形較多，於該情形時 表面粗糙度大之部位及表面粗糙度小之部位之粗糙度對最 終壓延之最終道次之板厚控制造成的影響有所不同，結果 導致該條件下之最終壓延板厚之不均增大。較佳為 0_025#m以下’更加為〇.〇2〇"m以下。 另一方面，於壓延銅羯中，於表面上存在大量與藉由 輥眼所決定之表面粗糙度不同之被稱作油坑（〇il ph)之壓延 銅箔特有之凹處。油坑為將壓延油擠壓至被壓延材料而產 生之凹處，表面上之油坑的密度依壓延油之油膜之厚度而 有所不同。若表面上之油坑之密度不同，則亦對以重量法 所求得之銅箔之板厚造成影響，成為不均之因素。因 期望油土几均勻分佈於銅箱表面上。 油坑之產生量，可以壓延平行方向之表面粗糙度RSm 作為指標。於RSm大之情形時表示表面上之油坑少於 小之情形時表示表面上之油坑之量多。對界定板厚精度： 201205931 成影響之原因在於：由於油坑之分佈之不均，故而以ΔΚδιη RSmmax ~ Rsmmin相對於壓延平行方向之表面粗糙度 之平均值（RSmavg )之比（△RSm/ RSmavg )作為指標。ARSm / RSmavg越小，則表示油坑於銅箔表面上分佈越均勻。除 以RSmavg之原因在於：分佈之不均中，即便大未必 不均必然大。即，例如：即便ΔΙΙδηι相同，若Μ%%大則 分佈之不均並不大因此其影響小，於RSmavg小之情形時分 佈之不均大因此影響大。 藉由加快壓延速度，提高壓延油之黏度，或減小每i 道次之壓下率而易於增加油坑之產生量，且減小RSm。相 反，藉由減慢壓延速度，降低壓延油之黏度，或增大每i 道次之壓下率而易於減少油坑之產生量，且增大RSm。 RSm係根據粗糙度曲線與平均線交叉之交點所求得之 凹點一週期之間隔的平均值，依據JIS B〇6〇1 : 2〇〇1而測 定。於本發明中表面粗縫度RSm之平均值（RSmavg)為任 意10點之平均值，係所測定之1〇點之Ra中，作為 最大值之RSmmax與作為最小值之RSn^n之差。其中，此處 所謂任意之10點’並非指各測定點相互處於附近之ι〇點， 例如若於線圈狀之情形時，則根據所得長度，以於壓延方 向至少為15〇_間隔、較佳為_mm間隔、更佳為1〇1間 隔以上選擇1 0點。各測定點中之RSm係由對測定點附近測 疋3次之平均值而得。再者，各測定點係選取寬度方向中 央之RSm。X，於將電池分解之情形時，即便為重疊有複 數個之負極用㈣之薄片若亦可確保150mm以上之測定間S 8 201205931 0.03"m above's better range is 〇〇3"msRas〇' and its characteristics are also: the reason that Ramn is 〇〇25^, and ARa--Ramjn is 0.025 vm is the condition: The copper foil after the final rolling of the product is 〇〇25 "01 or less', which means that the ARa before the final pass of the final rolling is 0.025 #m or less. If the ARa before the final pass of the final rolling is below 〇〇25 "claw, the influence on the thickness control will be less due to the unevenness (variation) of the surface roughness at the final pass of the final rolling. The plate thickness accuracy of the products in the pass is improved. When the ARa exceeds 0.025 // m, the ARA before the final pass of the final rolling is more than 〇·〇25 " m. In this case, the surface roughness is large and the surface roughness is small. The roughness has a different effect on the ultimate thickness control of the final pass, resulting in an increase in the unevenness of the final rolled sheet under this condition. Preferably, 0_025#m or less is more than 〇.〇2〇"m or less. On the other hand, in the rolled copper ruthenium, there are a large number of recesses on the surface which are specific to the rolled copper foil called a sump which is different from the surface roughness determined by the roll eye. The oil pit is a recess in which the rolling oil is extruded to the material to be calendered, and the density of the oil pit on the surface varies depending on the thickness of the oil film of the calendering oil. If the density of the oil pits on the surface is different, it also affects the thickness of the copper foil obtained by the gravimetric method, and becomes a factor of unevenness. Because the oil and soil are expected to be evenly distributed on the surface of the copper box. The amount of oil crater generated can be used as an index by rolling the surface roughness RSm in the parallel direction. When the RSm is large, it means that the amount of oil pits on the surface is less than that of the small one, indicating that the amount of oil pits on the surface is large. Accuracy of the defined plate thickness: 201205931 The reason for the influence is that the ratio of ΔΚδιη RSmmax ~ Rsmmin to the average of the surface roughness in the parallel direction of the rolling (RSmavg) due to the uneven distribution of the oil pits (ΔRSm/ RSmavg) ) as an indicator. The smaller the ARSm / RSmavg, the more uniform the oil sump is distributed on the surface of the copper foil. The reason for dividing by RSmavg is that in the uneven distribution, even if it is big, it is not necessarily uneven. In other words, for example, even if ΔΙΙδηι is the same, if Μ%% is large, the unevenness of distribution is not large, so the influence is small, and when RSmavg is small, the unevenness of distribution is large, so that the influence is large. It is easy to increase the amount of oil crater and reduce the RSm by speeding up the calendering speed, increasing the viscosity of the rolling oil, or reducing the reduction ratio per pass. Conversely, by slowing down the calendering speed, reducing the viscosity of the calendering oil, or increasing the reduction ratio per pass, it is easy to reduce the amount of crater generated and increase the RSm. The RSm is an average value of the interval of the pits obtained from the intersection of the roughness curve and the average line, and is measured in accordance with JIS B〇6〇1 : 2〇〇1. In the present invention, the average value (RSmavg) of the rough surface roughness RSm is an average value of any 10 points, which is the difference between the RSmmax which is the maximum value and the RSn^n which is the minimum value among the measured Ra points of 1 point. Here, the term "any 10 points" does not mean that the respective measurement points are in the vicinity of each other. For example, in the case of a coil shape, it is preferably at least 15 〇 intervals in the rolling direction according to the obtained length. Select 10 points for the _mm interval, more preferably for the 1〇1 interval. The RSm in each measurement point was obtained by averaging three times near the measurement point. Furthermore, each measurement point is selected from the RSm in the center of the width direction. X, when the battery is decomposed, it is possible to ensure a measurement of 150 mm or more even if a plurality of negative electrodes (4) are overlapped.
S 10 201205931 隔，則可對該薄片測定表面粗糙度。 於本發明之銅箔的較佳之一實施形態中，/ RSmavg 為 0.5 以下。 於本發明之銅箔的較佳之一實施形態中，銅箔之板厚 之最大值（tmax )與板厚之平均值（tavg )之差，或最小值（^ ) 與板厚之平均值（tavg)之差中之任意較大值相對於板厚 平均值（tavg )之比例可設為！ 3%以下。該比例較佳亦可設 為1.2%以下’更佳亦可設為1 1%以下。 繼而對本發明之銅落之製造方法進行說明。表面粗俨 度以之控制可藉由調整工作輥之表面粗饒度而進行例： 2使用Ra大之工作輥則所得壓延銅荡之Ra亦增大，相反 右使用Ra小之ji作報則所得塵延銅箱之Ra亦減小。另— :面，通常平均值較大者’不均值本身亦增大。對表面粗 、度Ra之不均值亦相同，表面粗链度以之平均值較大者， 不句值亦較大’因此為降低表面粗糙度之不均值，只要 減小表面粗糙度Ra之平均值即可。 /、 其中，於各種製品中，有根據與負極活性物質之密八 點而要求之表面粗糖度之要求，因此需要最爾 懕:i又，於冷軋中’就可將壓延速度設定成較高 佳。效率之觀點而言’表面粗糙度為某種程度之粗糙較 例如僅最終冷軋之最終道次前之 面粗糙度小夕τ从± Λ m人1之用衣 μ ^ 作輕’製作表面粗糙度小即表面平滑之銅 泊’於最終道次中蚀 人中使用表面粗糙度大之工作輥，製成所需 201205931 之表面粗縫度Ra。 藉此’可得到獲得高厚度精度的同時具有所需之表面 粗糙度且與活丨生物質之密合性良好之銅箔。即至最終道 -人之2道-人别為止利用表面粗糙度以粗糙之輥即可，僅最 終道ήά 1道次’使用較前道次及最終道次粗糙度更小 之輥。 不僅最、，、道_人刖之丨道次其之前之道次亦可使用表 面粗匕度小之工作觀’但表面粗糖度小之輕無法提高壓延 速度因此就生產性之觀點而言不理想。因此通常僅減小 最終道次前之道次所使用之工作輥之表面粗糙度。其中， 右’。視生產性之觀點’則最終道次前1道次更之前的道次 亦使用表面粗料小之親其降低表面粗糙度之不均之效果 較高。例如僅最終道次前之2道次使用表面粗 亦有效果。 f& ;最；道人中，工作輥使用表面粗糙度Ra超過〇〇1以 :者以使銅㈣延平行方向之以之平均值〜)為〇.〇1 0.15二m ’因此為減小表面㈣度之不均值’最終道次前 之1道-人所使用之工作輥之表面粗糙度Ra必需比於最 次所使用之工作輥更小°因此，最終道次前之丨道次所使 用之工作輥之表面粗糙度Ra較理想為〇 〇1仁m以下。 然而，穩定製作表面粗糙度⑸為〇〇1"m以下且 ::傷等之外觀上的問題之觀，需要較高的技術，且二 費方面亦相對地變高。 、匕 因此，更佳的範圍係於最終道次中所使用的工作親其 12 201205931 表面：糙度Ra為0.03_以上為較佳因此使用於最終 道次前1個道次之工你故从主：， 作輥的表面粗糙度Ra較佳為未達〇.〇3 以m。 …為降低表面粗縫度RSm之不均，使油坑之分佈均句變 付重要。為使油坑之公你& 佈句勻’在若干之因素中將壓延油 之黏度於壓延過鞋Φ仅^主m 一 '、持固疋亦為重要。壓延油之黏度基 本上根據壓延油之種類而決定，由於因壓延過程中之加工 熱而使壓延油緩镑弁、、® μ工+ 攱升/m從而使黏度降低。若伴隨壓延油之 黏度之變化，壓延油壓入銅箱表面之程度發生變化，則導 致油坑分佈之不均。 例如壓延油於壓延前之溫度調整時保持在25t左右 時右將壓延油噴射至壓延過程中之工作親則由因加工執 而升溫之工作輥等之熱量會傳導，壓延油升溫i 口、 右。若可維持在該狀態，則油坑之分佈之不均少，對㈣ 形狀不會產生問題 '然而’於壓延油之溫度控制不充分， 壓延油溫度㈣贼而發生不均之情形時，不僅㈣之表 面性狀容易發生不均’亦會對板形狀造成影響。因此 將壓延過程中之壓延油之溫度調整至贼左右，必需综合 性调整輥喷射前之壓延油溫度、壓延速度、加工度等。 可使用藉由以本發明之壓延銅羯為材料之集電器及形 成於其上之活性物f所構成之負極，並利用慣用方法來製 =離子電池。於鐘離子電池中，包含電解質中之链離子 、貝導電之鐘離子-次電池及鐘離子二次電池。負極活性 物質，並無限制，可列舉：碳、矽、錫、鍺、鉛、銻、鋁、 13 201205931 銦、鋰、氧化錫、鈦酸鋰、氮化鋰、將銦固 銦-錫合金、鐘—紹合金、經—銦合金等。氧化錫、 [實施例] 以下表示本發明之實施例，但該等係為更好地理解本 發明而提供’並非旨在對本發明進行限定。 <例1 (表面粗糙度Ra之不均之影響）> [壓延銅箔之製造] 將精銅之鑄錠熱軋後，反覆退火及冷軋，最終進行冷 軋，獲得壓延方向長度為1Gm以上且設定厚纟⑺心之壓 延銅箔（No. 1〜6 )。於最終冷軋中，僅於最終道次前i道 次使用之工作輥之表面粗糙度，及最終道次所使用之工作 輥之表面粗糙度示於表卜所使用之壓延油之黏度為7 (4〇 C )，最終冷軋中之壓延油之溫度控制在4〇c>c左右。工 作輥之表面粗糙度依據JIS B0601 : 2〇〇1，以接觸式之表面 粗糙度計進行測定。 將所獲得之壓延銅荡放置並固定於玻璃板上’使用 Lasertec公司之共軛焦顯微鏡（confod m1Croscope)HD100D，基於上述測定方法算出Ra^、△&、 RSmavg、及△RSm。結果示於表1。 [板厚精度評價] 壓延銅箔之板厚依據重量法（IPC_TM—65〇)進行測 疋。自所獲得之銅箔選擇任意之丨〇m之壓延方向長度，對 此以1 m間隔測定10點板厚。各測定點之板厚τ採取3次 測定之平均值《將10點之τ之平均值設為Tavg、1〇點之τS 10 201205931 The surface roughness of the sheet can be measured. In a preferred embodiment of the copper foil of the present invention, /RSmavg is 0.5 or less. In a preferred embodiment of the copper foil of the present invention, the difference between the maximum value (tmax) of the thickness of the copper foil and the average value (tavg) of the sheet thickness, or the minimum value (^) and the average value of the sheet thickness ( The ratio of any larger value of the difference between tavg) and the plate thickness average (tavg) can be set! Less than 3%. The ratio may preferably be set to 1.2% or less, and more preferably set to be 1% or less. Next, a method of manufacturing the copper drop of the present invention will be described. The surface roughness can be controlled by adjusting the surface roughness of the work roll. 2 The Ra of the work roll of Ra is increased by Ra, and the Ra is increased by Ra. The Ra of the resulting dust-extended copper box is also reduced. Another - : face, usually the larger the average 'the average value itself is also increased. The unevenness of the surface roughness and degree Ra is also the same. If the average value of the surface thick chain is larger, the value of the surface is larger. Therefore, in order to reduce the unevenness of the surface roughness, the average of the surface roughness Ra is reduced. The value is fine. /, Among them, in various products, there is a requirement for the surface roughness of the surface according to the density of the negative electrode active material, so it is required to be the most desirable: i, in cold rolling, the calendering speed can be set to be Gao Jia. From the viewpoint of efficiency, the surface roughness is a certain degree of roughness. For example, only the surface roughness before the final pass of the final cold rolling is small, and the surface roughness is made from ± Λ m. The small surface, that is, the surface smooth copper berth, is used in the final pass, and the work roll having a large surface roughness is used to form the surface roughness Ra of the desired 201205931. By this, it is possible to obtain a copper foil which has high surface precision and which has a desired surface roughness and which is excellent in adhesion to living biomass. That is to say, the final road - the two people - the person to use the surface roughness with a rough roller, only the last pass ήά 1 pass 'use a roll with a smaller roughness than the previous pass and the final pass. Not only the most,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ideal. Therefore, it is usually only necessary to reduce the surface roughness of the work rolls used in the pass before the final pass. Among them, right'. Depending on the point of view of productivity, the last pass of the previous pass also uses the surface coarse material to reduce the unevenness of the surface roughness. For example, it is also effective to use the rough surface only for the 2 passes before the final pass. f&;most; in the Taoist, the work roll uses a surface roughness Ra exceeding 〇〇1 to: the copper (four) is extended in parallel with the average value ~) 〇.〇1 0.15二m ' (4) Degree of unevenness 'Before the final pass - the surface roughness Ra of the work roll used by the person must be smaller than the work roll used at the last time. Therefore, the last pass before the pass is used. The surface roughness Ra of the work rolls is preferably less than or equal to 1 ren. However, the stable production of the surface roughness (5) is a problem of the appearance of 〇〇1 "m and below, and the like, and a higher technique is required, and the second aspect is relatively high. Therefore, the better range is the work used in the final pass. 12 201205931 Surface: Roughness Ra is 0.03_ or more is preferred. Therefore, it is used in the first pass of the final pass. Main: The surface roughness Ra of the roller is preferably less than 〇.〇3 in m. ...In order to reduce the unevenness of the surface roughness RSm, it is important to make the distribution of the oil pits uniform. In order to make the sump of the sump you & suffices in a number of factors, the viscosity of the rolling oil is rolled over the shoe Φ only ^ main m a ', holding the solid is also important. The viscosity of the rolling oil is basically determined by the type of the rolling oil, and the rolling oil is lowered by the processing heat during the rolling process, and the viscosity is lowered by increasing the viscosity of the rolling oil. If the viscosity of the rolling oil is changed to the surface of the copper box with the change in the viscosity of the rolling oil, the uneven distribution of the oil sump is caused. For example, when the temperature of the rolling oil is maintained at about 25t during the temperature adjustment before rolling, the right side of the rolling oil is injected into the calendering process. The heat of the work rolls heated by the processing is transmitted, and the rolling oil is heated to the mouth, right. . If it can be maintained in this state, the distribution of the oil pits is less uneven, and there is no problem with the shape of (4). However, when the temperature control of the rolling oil is insufficient, and the rolling oil temperature (4) is uneven, the (4) The surface properties are prone to unevenness, which also affects the shape of the board. Therefore, the temperature of the rolling oil during the rolling process is adjusted to the thief, and it is necessary to comprehensively adjust the rolling oil temperature, rolling speed, and degree of processing before the roll is sprayed. An anode composed of the current collector of the rolled copper crucible of the present invention and the active material f formed thereon can be used, and an ion battery can be produced by a conventional method. In the ion battery, a chain ion in a electrolyte, a bell-electrode ion-sub-battery, and a clock-ion secondary battery are included. The negative electrode active material is not limited, and examples thereof include carbon, antimony, tin, antimony, lead, antimony, and aluminum. 13 201205931 Indium, lithium, tin oxide, lithium titanate, lithium nitride, indium-fixed indium-tin alloy, Zhong-Shao alloy, warp-indium alloy, etc. [Examples] The following examples of the invention are intended to provide a better understanding of the invention and are not intended to limit the invention. <Example 1 (Impact of unevenness of surface roughness Ra)> [Production of rolled copper foil] After hot-rolling of the ingot of the refined copper, it is subjected to reverse annealing and cold rolling, and finally cold rolling is performed to obtain a length in the rolling direction. A rolled copper foil (No. 1 to 6) of 1 gm or more and a thick 纟 (7) core is set. In the final cold rolling, the surface roughness of the work rolls used only in the last pass of the final pass, and the surface roughness of the work rolls used in the final pass are shown in Table 5. The viscosity of the rolled oil used in the table is 7 (4〇C), the temperature of the rolling oil in the final cold rolling is controlled at about 4〇c>c. The surface roughness of the work rolls was measured in accordance with JIS B0601: 2〇〇1 using a contact surface roughness meter. The obtained rolled copper was placed and fixed on a glass plate. Ra^, Δ &, RSmavg, and ΔRSm were calculated based on the above-described measurement method using a confocal microscope (HDCDD) of Lasertec Co., Ltd. The results are shown in Table 1. [Evaluation of plate thickness accuracy] The thickness of the rolled copper foil was measured by the gravimetric method (IPC_TM - 65 〇). The length of the rolling direction of any 丨〇m was selected from the obtained copper foil, and the thickness of 10 points was measured at intervals of 1 m. The plate thickness τ of each measurement point is taken three times. The average value of the measurement is "the average value of τ of 10 points is set to Tavg, 1 〇 τ
S 14 201205931 之最大值設為Tniax、10點之τ之最小值設為Tmin。於表i 中將（Tavg—Tmin) /Tavg 及（Tmax—Tavg) /Tavg 之較大者 記述為「板厚不均（％)」。The maximum value of S 14 201205931 is set to Tniax, and the minimum value of τ of 10 points is set to Tmin. In Table i, the larger of (Tavg - Tmin) / Tavg and (Tmax - Tavg) / Tavg is described as "plate thickness unevenness (%)".
No.l〜Νο·4為發明例，能夠將板厚之不均抑制為13% 以下。 Νο.5係最終道次前之丨道次之表面粗糙度大，因此無 法充分控制ARa。No.6中，雖減小最終道次之工作輥之表 面粗糙度’代替增大最終道次前1道次之工作輥之表面粗 縫度’但依然無法充分控制△&。 [表1] 工作輥表面粗糙度RaNo. 1 to Ν ο 4 are examples of the invention, and the unevenness of the sheet thickness can be suppressed to 13% or less. Νο.5 is the surface roughness of the gongs before the final pass, so the ARa cannot be fully controlled. In No. 6, although the surface roughness of the work roll of the final pass was reduced, instead of increasing the surface roughness of the work roll before the last pass, the Δ& [Table 1] Work Roller Surface Roughness Ra
<例2 (油坑之分佈之影響）> [壓延銅箔之製造] 將精銅之鑄錠熱軋後，反覆退火及冷軋，最終進行冷 札’獲得壓延方向長度為l〇m以上且設定厚度1〇以爪之壓 延銅箔（Νο·7〜12 )。於最終冷軋中，將直至最終道次前所 使用之工作輥表面粗糙度Ra設為〇.〇 1 〇从m，及將最終道·欠 所使用之工作輥表面粗糙度Ra設為0.050 // m。所使用之壓 延油之黏度為7.0cSt ( 40°C )，發明例係將最終冷軋中之壓 15 201205931 相同 埋 不 延油之溫度調整為40t左右。各種特性評價以與例 之方法進行。試驗結果示於表2。 之壓延油之溫度督 不均較少、板厚之 發明例Νο·7〜9係將最終壓延機 管理為40 C ’因此油坑之分佈均勾、 均為小至未達1.2 %。 發明例Ν〇·10〜12巾，除最終冷乳機中之壓延油之溫 度管理以外’以與發明w Νο·7〜9相同之條件來實施。2 處未充分進行最終冷軋機中之壓延油之溫度的管理，因此 超過40 C升溫至45 C左右。雖於測定時未能確認，但推測 亦有局部超過50°C之部分。其結果，發現無法使油坑之分 佈均勻化、板厚之不均超過丨2%之實例。<Example 2 (Impact of distribution of oil pits)> [Manufacture of rolled copper foil] After hot-rolling of ingots of refined copper, it is repeatedly annealed and cold-rolled, and finally cold-rolled to obtain a rolling direction length of l〇m Above and set a rolled copper foil (Νο·7~12) with a thickness of 1〇. In the final cold rolling, the surface roughness Ra of the work rolls used before the final pass is set to 〇.〇1 〇 from m, and the surface roughness Ra of the work rolls used for the final pass is set to 0.050 / / m. The viscosity of the calendering oil used was 7.0 cSt (40 ° C), and the invented example adjusted the temperature of the final cold rolling to 15 201205931 and the temperature of the same non-expansion oil to about 40 tons. Various characteristic evaluations were carried out by way of example. The test results are shown in Table 2. The temperature of the rolling oil is not uniform, and the thickness of the invention is 发明ο·7~9. The final calender is managed as 40 C ′ so the distribution of the oil pits is as small as less than 1.2%. Inventive Example 10 to 12, except for the temperature management of the rolling oil in the final cold milk machine, was carried out under the same conditions as the inventions w Νο·7 to 9. The management of the temperature of the rolling oil in the final cold rolling mill was not sufficiently carried out at 2 places, so the temperature was raised to about 45 C over 40 C. Although it was not confirmed at the time of measurement, it is presumed that there is a portion partially exceeding 50 °C. As a result, it was found that the distribution of the oil sump could not be uniformized, and the unevenness of the thickness of the sheet exceeded 丨2%.
S 16 201205931 【<Ν<】S 16 201205931 [<Ν<]
板厚不均ι 0.09 1.03 I 1 121 1 1.22 1.23 | ARSm/平 均RSm 0.500 0.389 0.400 0.643 0.611 0.700 ARSm B 寸 r—< 00 τ—Η 〇〇 CS RsiTlmin βχη CN (N m m 〇 m 1 RSlllmax I Β m CN CN 00 η 00 平均RSm μνη 00 CN 00 1—^ 〇 00 Oi 〇〇 ο ARa μτη 0.018 0.023J 0.019 0.023 J 0.02 1 0.02 1 R^min Β 0.055 0.046 0.043 1 0.045 1 1 0.043 1 0.041 1 I RS-max I βτη 0.073 0.069 0.062 0.068 0.063 0.061 1 |平均Ra βτη 0.064 0.058 0.054 0.062 0.053 0.054 壓延油溫度 Ρ 〇 〇 >40 >40 >40 區分 發明例 |發明例| 發明例 發明例 發明例 發明例ι 6 卜 〇〇 ON Ο CN - 201205931 【圖式簡單說明】 無 【主要元件符號說明 無Uneven thickness ι 0.09 1.03 I 1 121 1 1.22 1.23 | ARSm/average RSm 0.500 0.389 0.400 0.643 0.611 0.700 ARSm B-inch r-< 00 τ-Η 〇〇CS RsiTlmin βχη CN (N mm 〇m 1 RSlllmax I Β m CN CN η η 00 Average RSm μνη 00 CN 00 1—^ 〇00 Oi 〇〇ο ARa μτη 0.018 0.023J 0.019 0.023 J 0.02 1 0.02 1 R^min Β 0.055 0.046 0.043 1 0.045 1 1 0.043 1 0.041 1 I RS -max I βτη 0.073 0.069 0.062 0.068 0.063 0.061 1 |Average Ra βτη 0.064 0.058 0.054 0.062 0.053 0.054 Calendering oil temperature Ρ 〇〇>40 >40 >40 Distinction Example | Invention Example | Invention Example Invention Example Invention Invention Example ι 6 卜〇〇ON Ο CN - 201205931 [Simple description of the diagram] No [Main component symbol description No