TWI455394B - Copper foil for lithium ion battery collectors - Google Patents

Copper foil for lithium ion battery collectors Download PDF

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TWI455394B
TWI455394B TW100109833A TW100109833A TWI455394B TW I455394 B TWI455394 B TW I455394B TW 100109833 A TW100109833 A TW 100109833A TW 100109833 A TW100109833 A TW 100109833A TW I455394 B TWI455394 B TW I455394B
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copper foil
lithium ion
surface roughness
current collector
thickness
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TW100109833A
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TW201205931A (en
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Shutaro Nishida
Daisuke Samejima
Kaichiro Nakamuro
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Jx Nippon Mining & Metals Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Metal Rolling (AREA)

Description

鋰離子電池集電器用銅箔Copper foil for lithium ion battery collector

本發明係關於一種鋰離子電池集電器用銅箔，尤其關於一種鋰離子二次電池負極集電器用銅箔。The present invention relates to a copper foil for a lithium ion battery current collector, and more particularly to a copper foil for a lithium ion secondary battery negative electrode current collector.

鋰離子電池具有能量密度高、可獲得較高之電壓之特徵，多用於筆記型電腦、攝影機、數位相機、行動電話等小型電子機器。認為將來亦有希望用作電動汽車或普通家庭之分散配置型電源此類大型機器之電源。Lithium-ion batteries are characterized by high energy density and high voltage, and are used in small electronic devices such as notebook computers, video cameras, digital cameras, and mobile phones. It is believed that there will be a power source for large machines such as distributed electric power sources for electric vehicles or ordinary households.

鋰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。通常，正極係由鋁箔所製成之正極集電器與設置於其表面之LiCoO2 、LiNiO2 及LiMn2 O4 等鋰複合氧化物作為材料之正極活性物質所構成，負極係由以銅箔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。The electrode body of a lithium ion battery generally has a stacked structure in which a positive electrode, a separator, and a negative electrode are wound or laminated in several layers. Usually, the positive electrode is composed of a positive electrode current collector made of an aluminum foil and a lithium composite oxide such as LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 provided on the surface thereof as a positive electrode active material of the material, and the negative electrode is made of a copper foil. The negative electrode current collector and the negative electrode active material which is a material coated on the surface of the negative electrode current collector are used.

用作負極集電器之銅箔之重要課題有其與負極活性物質之密合性，先前以提昇該密合性為中心而對集電器用銅箔進行研究開發。用以改善與活性物質之密合性之一般方法，可舉稱為事先粗化處理之於銅箔表面形成凹凸的表面處理。粗化處理之方法，已知有噴砂處理、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之鍍敷等方法，該等之中，特別以電沉積粒子之鍍敷最為常用。該技術，係為了下述目的而進行：使用硫酸銅酸性鍍敷浴，於銅箔表面將銅電沉積為多數之樹枝狀或小球狀，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，防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3733067號公報)。An important problem of the copper foil used as the negative electrode current collector is the adhesion to the negative electrode active material, and the copper foil for current collectors has been researched and developed mainly to improve the adhesion. The general method for improving the adhesion to the active material may be referred to as a surface treatment for forming irregularities on the surface of the copper foil by a roughening treatment in advance. As a method of roughening treatment, a sandblasting treatment, rolling by a rough roll, mechanical grinding, electrolytic grinding, chemical polishing, and plating of electrodeposited particles are known, among which, particularly, electrodeposited particles are used. Plating is most commonly used. This technique is carried out for the purpose of using a copper sulfate acid plating bath to electrodeposit copper on the surface of a copper foil into a plurality of dendrites or small balls to form fine concavities and convexities, and to obtain adhesion by a quasi-effect. When the active material is expanded in a large volume, the stress is concentrated on the concave portion of the active material layer to form a crack, and the peeling due to stress concentration at the interface of the current collector is prevented (for example, Japanese Patent No. 3733067) .

於日本專利第3733065號公報中，揭示有以粗糙度之參數來具體界定較佳之表面性狀，並藉由將表面粗糙度Ra之值大之銅箔用作為集電器，提昇集電器與活性物質之密合性(段落0209)。集電器之表面粗糙度Ra較佳為0.01μm以上，更佳為0.01～1μm，進而更佳為0.05～0.5μm(段落0021等)。集電器之表面粗糙度Ra與局部頂端之平均間隔S較佳為具有100Ra≧S之關係(段落0022等)。集電器表面之凹凸之凸部的形狀較佳為錐體狀(段落0023等)。In Japanese Patent No. 3733065, it is disclosed that a preferred surface property is specifically defined by a parameter of roughness, and a copper foil having a large surface roughness Ra is used as a current collector to enhance the current collector and the active material. Adhesion (paragraph 0209). The surface roughness Ra of the current collector is preferably 0.01 μm or more, more preferably 0.01 to 1 μm, still more preferably 0.05 to 0.5 μm (paragraph 0021, etc.). The average interval S between the surface roughness Ra of the current collector and the local tip is preferably 100 Ra ≧ S (paragraph 0022, etc.). The shape of the convex portion of the unevenness on the surface of the current collector is preferably a cone shape (paragraph 0023, etc.).

並且揭示有該類表面形態可以於電解銅箔(段落0044)、藉由電解法使銅析出於壓延銅箔之表面而將表面粗化(段落0045)，及以砂紙進行研磨處理(段落0205)而獲得。It is also disclosed that such surface morphology can be used to electrolyze copper foil (paragraph 0044), to roughen the surface of the copper foil by electrolytic deposition (paragraph 0045), and to grind with sandpaper (paragraph 0205). And get.

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

[專利文獻2]日本專利第3733065號公報[Patent Document 2] Japanese Patent No. 3733065

鋰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，但現狀為負極活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銅箔之重量而進行。因此，若不固定作為集電器之銅箔之厚度則無法適當管理應塗佈之負極活性物質之量。銅箔之比重約為8.92g/cm3 ，用作負極活性物質之碳之比重約為0.5g/cm3 ，故而例如相當於銅箔之厚度0.1μm的碳之厚度為1.78μm。因此，於以厚度10μm為目標製造銅箔時厚度僅有0.1μm(1.00%)之不均，會使碳之厚度產生高達1.78μm(於以厚度40μm為目標之情形時相當於4.45%)之誤差。其於40μm厚度之活性物質中，相當於4.45%之不均。即結果為銅箔之微小厚度之不均會對活性物質之厚度造成較大影響。因此期望板厚精度優異之銅箔。Since the battery capacity of the lithium ion battery changes depending on the coating amount of the negative electrode active material, it is important to control and manage the coating amount of the negative electrode active material in order to stabilize the battery characteristics, but the current state is the coating of the negative electrode active material. The management of the coating amount in the cloth step is carried out according to the weight of the copper foil after coating. Therefore, if the thickness of the copper foil as the current collector is not fixed, the amount of the negative electrode active material to be applied cannot be properly managed. The proportion of copper is approximately 8.92g / cm 3, is used as the negative electrode active material of a specific gravity of carbon is about 0.5g / cm 3, for example, therefore corresponds to the thickness of the carbon of a copper foil thickness of 0.1μm was 1.78μm. Therefore, when the copper foil is manufactured with a thickness of 10 μm, the thickness is only 0.1 μm (1.00%), and the thickness of the carbon is as high as 1.78 μm (equivalent to 4.45% when the thickness is 40 μm). error. It is equivalent to 4.45% unevenness in the active material having a thickness of 40 μm. That is, the result is that the uneven thickness of the copper foil has a large influence on the thickness of the active material. Therefore, a copper foil excellent in sheet thickness precision is desired.

然而，集電器用銅箔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。因此，以宏觀觀點提昇銅箔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。However, the development direction of copper foil for current collectors has been overwhelmingly controlled by surface properties, which is a microscopic viewpoint for improving the adhesion to the negative electrode active material. Therefore, the problem of improving the capacitance stability of a lithium ion battery by improving the plate thickness precision of the copper foil from a macroscopic viewpoint has not yet been solved.

因此，本發明之課題之一在於提供一種板厚精度高之鋰離子電池集電器用銅箔。又，本發明之其他課題之一在於提供該種銅箔之製造方法。Therefore, one of the problems of the present invention is to provide a copper foil for a lithium ion battery current collector having high plate thickness precision. Further, another object of the present invention is to provide a method for producing such a copper foil.

銅箔大致分為壓延銅箔及電解銅箔。於壓延銅箔中，板厚精度多取決於壓延機之功能(能力)，而對於現狀之壓延機，於以板厚精度為目標之板厚10μm中±1.6%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。The copper foil is roughly classified into a rolled copper foil and an electrolytic copper foil. In the rolled copper foil, the accuracy of the plate thickness is largely determined by the function (capacity) of the calender, and the calender of the current state is limited to ±1.6% of the plate thickness of 10 μm which is the target 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.

本發明人在上述情況下，為解決上述課題而反覆研究，結果於壓延銅箔之製造過程中，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(final pass)前的表面粗糙度之不均係對板厚控制造成影響之因素之一，著眼於上述情況，發現於最終道次之前階段中減小表面粗糙度，並減小表面粗糙度之不均，藉此提昇板厚精度。具體而言，明白藉由於最終道次前之壓延中使用表面粗糙度小之工作輥，於最終道次中使用所需之表面粗糙度之工作輥，最終可獲得板厚精度良好、具有所需之表面粗糙度之銅箔。就考慮與活性物質之密合性之關係而言，於集電器用銅箔中要求特定之表面粗糙度，但藉由於最終冷軋之最終道次前預先儘可能減小表面粗糙度，可於提高板厚精度的同時具有所需之表面粗糙度。In the above case, the inventors of the present invention have repeatedly studied in order to solve the above problems. As a result, in the process of manufacturing a rolled copper foil, the rolling is mostly controlled by the thickness of the feedforward. Therefore, regarding the thickness accuracy of the product, the final cold rolling is finally completed. The unevenness of the surface roughness before the final pass is one of the factors affecting the thickness control. Focusing on the above situation, it is found that the surface roughness is reduced and the surface roughness is reduced in the stage before the final pass. The unevenness is used to improve the plate thickness accuracy. Specifically, it is understood that by using a work roll having a small surface roughness in the rolling before the final pass, the work roll having the required surface roughness is used in the final pass, and finally, the plate thickness precision is good and required. Copper foil with surface roughness. Considering the relationship with the adhesion of the active material, a specific surface roughness is required in the copper foil for the current collector, but the surface roughness can be reduced as much as possible before the final pass of the final cold rolling. Improve the thickness accuracy while having the required surface roughness.

以上述認識為基礎而完成之本發明於一態樣中，為一種鋰離子電池集電器用銅箔，其係壓延平行方向之表面粗糙度Ra之平均值(Raavg )為0.01～0.15μm，ΔRa=Ramax -Ramin 為0.025μm以下。The present invention, which is based on the above findings, is a copper foil for a lithium ion battery current collector having a mean value (Ra avg ) of a surface roughness Ra in a direction parallel to the rolling of 0.01 to 0.15 μm. ΔRa = Ra max - Ra min is 0.025 μm or less.

於本發明之鋰離子電池集電器用銅箔之一實施形態中，銅箔之板厚為5～20μm。In one embodiment of the copper foil for a lithium ion battery current collector of the present invention, the copper foil has a thickness of 5 to 20 μm.

於本發明之鋰離子電池集電器用銅箔之另一實施形態中，銅箔之板厚之最大值(tmax )與板厚之平均值(tavg )之差，或最小值(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1.3%以下。In another embodiment of the copper foil for a lithium ion battery current collector of the present invention, the difference between the maximum thickness (t max ) of the copper foil and the average value (t avg ) of the plate thickness, or the minimum value (t min) any larger value of the difference) and the average value (t avg) of an average value of the thickness of the sheet thickness (t avg) ratio of 1.3% or less.

於本發明之鋰離子電池集電器用銅箔之一實施形態中，ΔRSm=RSmmax -RSmmin 對於壓延平行方向之表面粗糙度RSm之平均值(RSmavg )之比(ΔRSm/RSmavg )為0.5以下。In one embodiment of the copper foil for a lithium ion battery current collector of the present invention, the ratio (ΔRSm/RSm avg ) of ΔRSm=RSm max −RSm min to the average value (RSm avg ) of the surface roughness RSm in the rolling parallel direction is (ΔRSm/RSm avg ) 0.5 or less.

於本發明之鋰離子電池集電器用銅箔之其他一實施形態中，銅箔為鋰離子二次電池負極集電器用。In another embodiment of the copper foil for a lithium ion battery current collector of the present invention, the copper foil is used for a lithium ion secondary battery negative electrode current collector.

本發明於其他一態樣中為一種具備本發明之銅箔作為集電器之鋰離子電池。In another aspect of the invention, a lithium ion battery having the copper foil of the invention as a current collector is used.

本發明進而於其他一態樣中，為一種鋰離子電池集電器用銅箔之製造方法，其係於最終冷軋步驟中，用於最終道次之工作輥之表面粗糙度Ra為0.03μm以上，用於最終道次前之1道次之工作輥之表面粗糙度Ra未達0.03μm。In another aspect, the present invention is a method for producing a copper foil for a lithium ion battery current collector, which is used in the final cold rolling step, and the surface roughness Ra of the work roll for the final pass is 0.03 μm or more. The surface roughness Ra of the work rolls for the first pass before the final pass was less than 0.03 μm.

本發明之銅箔係板厚精度優異，因此能夠抑制負極活性物質之塗佈量之誤差，從而可實現量產之鋰離子電池之電池電容之穩定化。Since the copper foil system of the present invention has excellent thickness precision, it is possible to suppress the error in the amount of application of the negative electrode active material, and it is possible to stabilize the battery capacity of the mass-produced lithium ion battery.

於本發明中使用之銅箔基材為壓延銅箔。「銅箔」中亦包含銅合金箔。銅箔之材料，並無特別限制，只要根據用途或要求特性進行適當選擇即可。例如，雖然無限定，但除高純度之銅(無氧銅或精銅等)之外，亦可列舉添加有Sn、Ag、Fe、In、Te等之銅合金，添加有Ni、Si等之Cu-Ni-Si系銅合金，添加有Cr、Zr等之Cu-Zr系、Cu-Cr-Zr系銅合金之類之銅合金。壓延銅箔於強度高、可應對連續發生振動之環境、耐彎曲性高之方面優異。The copper foil substrate used in the present invention is a rolled copper foil. Copper foil is also included in "copper foil". The material of the copper foil is not particularly limited, and may be appropriately selected depending on the use or characteristics required. For example, although it is not limited, in addition to high-purity copper (such as oxygen-free copper or refined copper), a copper alloy to which Sn, Ag, Fe, In, Te, or the like is added may be added, and Ni, Si, or the like may be added. A Cu-Ni-Si-based copper alloy is added with a copper alloy such as a Cu-Zr-based or a Cu-Cr-Zr-based copper alloy such as Cr or Zr. The rolled copper foil is excellent in strength, in an environment where vibration is continuously generated, and in high bending resistance.

銅箔之厚度並無特別限制，只要根據要求特性進行適當選擇即可。通常為1～100μm，於用作鋰離子二次電池負極之集電器之情形時，使銅箔厚度變薄可獲得更高電容之電池。就上述觀點而言，較典型為2～50μm，更典型為5～20μm左右。The thickness of the copper foil is not particularly limited, and may be appropriately selected according to the required characteristics. Usually, it is 1 to 100 μm. When used as a current collector for a negative electrode of a lithium ion secondary battery, the thickness of the copper foil is made thin to obtain a battery having a higher capacitance. From the above viewpoints, it is more typically from 2 to 50 μm, more typically from about 5 to 20 μm.

本發明之銅箔係根據壓延平行方向之表面粗糙度Ra之平均值(Raavg )，及ΔRa=Ramax -Ramin 而規定。Ra為將粗糙度曲線自中心線對折，將該粗糙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JISB0601：2001而測定。於本發明中所謂表面粗糙度Ra之平均值(Raavg )為任意10點之平均值，於本發明中所謂ΔRa係所測定之10點之Ra中，作為最大值之Ramax 與作為最小值之Ramin 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10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150mm間隔、較佳為400mm間隔、更佳為1m間隔以上選擇10點。各測定點中之Ra係由對測定點附近測定3次之平均值而得。再者，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150mm以上之測定間隔，則可對該薄片測定表面粗糙度。The copper foil of the present invention is defined by the average value (Ra avg ) of the surface roughness Ra in the rolling parallel direction and ΔRa = Ra max -Ra min . Ra is a value obtained by dividing the roughness curve from the center line and dividing the roughness curve and the area obtained by the center line by the reference length L, and measuring according to JIS B0601:2001. In the present invention, the average value (Ra avg ) of the surface roughness Ra is an average value of any ten points. In the Ra of 10 points measured by the ΔRa system in the present invention, Ra max as a maximum value and a minimum value. The difference between the Ra min . Here, the arbitrary ten points herein do not mean that each of the measurement points is in the vicinity of 10 points. For example, in the case of a coil shape, the length is set to be at least 150 mm intervals in the rolling direction, preferably 400 mm. It is better to select 10 points for the interval of 1 m or more. The Ra system in each measurement point was obtained by measuring the average value of three times in the vicinity of the measurement point. Furthermore, each measurement point is selected from the center of the width direction Ra. Further, in the case where the battery is decomposed, even if a plurality of sheets of the copper foil for negative electrode are stacked, if the measurement interval of 150 mm or more can be secured, the surface roughness can be measured.

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0.01～0.15μm。以0.01μm≦Ra≦0.15μm作為條件之原因在於：若Ra未達0.01μm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0.15μm，則即便藉由最終道次前之壓延而減小粗糙度，使表面粗糙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0.03μm以上，更佳之範圍為0.03μm≦Ra≦0.1μm。The copper foil of the present invention is characterized in that the average value (Ra avg ) of the surface roughness Ra in the direction parallel to the rolling is satisfied to 0.01 to 0.15 μm. The reason why 0.01 μm ≦Ra ≦ 0.15 μm is used is that if Ra is less than 0.01 μm, the surface is smooth and sufficient adhesion to the negative electrode active material cannot be obtained, and if it exceeds 0.15 μm, even if it exceeds 0.15 μm The rolling before the final pass reduces the roughness, making the surface roughness less uneven, and also causing unevenness due to the final pass rolling. However, in view of stabilizing the appearance quality in which surface defects such as surface flaws are small, it is desirable that Ra is 0.03 μm or more, and more preferably 0.03 μm ≦Ra ≦ 0.1 μm.

又，其特徵亦在於：滿足△Ra=Ramax -Ramin 為0.025μm以下。以△Ra=Ramax -Ramin 為0.025μm作為條件之原因在於：若作為製品之最終壓延後之銅箔的△Ra為0.025μm以下，則意味著最終壓延之最終道次前之△Ra為0.025μm以下。若最終壓延之最終道次前之△Ra為0.025μm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△Ra超過0.025μm之情形時，最終壓延之最終道次前之△Ra超過0.025μm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。△Ra較佳為0.025μm以下，更加為0.020μm以下。Further, it is characterized in that ΔRa = Ra max - Ra min is satisfied to be 0.025 μm or less. The reason why ΔRa=Ra max -Ra min is 0.025 μm is that if the ΔRa of the copper foil after the final rolling of the product is 0.025 μm or less, it means that the ΔRa before the final pass of the final rolling is Below 0.025 μm. If the ΔRa before the final pass of the final rolling is 0.025 μm or less, the influence on the thickness control due to the unevenness (variation) of the surface roughness at the final pass of the final rolling is small, that is, in the final pass. The thickness of the product is improved. When the ΔRa exceeds 0.025 μm, the ΔRa before the final pass of the final rolling exceeds 0.025 μm, and in this case, the roughness of the portion having a large surface roughness and the portion having a small surface roughness is finally The effect of the plate thickness control of the final pass of the calendering is different, resulting in an increase in the uneven thickness of the final calendered sheet under this condition. ΔRa is preferably 0.025 μm or less, and more preferably 0.020 μm or less.

另一方面，於壓延銅箔中，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(oil pit)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。因此，期望油坑均勻分佈於銅箔表面上。On the other hand, in the rolled copper foil, there are a large number of recesses on the surface which are specific to the rolled copper foil called an oil pit which is different from the surface roughness determined by the roll eye. The oil pit is a recess formed by pressing the rolling oil 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. Therefore, it is desirable that the oil sump be evenly distributed on the surface of the copper foil.

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RSm小之情形時表示表面上之油坑之量多。對界定板厚精度造 成影響之原因在於：由於油坑之分佈之不均，故而以△RSm=RSmmax -RSmmin 相對於壓延平行方向之表面粗糙度RSm之平均值(RSmavg )之比(△RSm/RSmavg )作為指標。△RSm/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△RSm大未必不均必然大。即，例如：即便△RSm相同，若RSmavg 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。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 there are few oil pits on the surface, and when the RSm is small, it means that the amount of oil pits on the surface is large. The reason for the influence on the accuracy of the defined plate thickness is that the ratio of ΔRSm=RSm max -RSm min to the average value of the surface roughness RSm (RSm avg ) in the parallel direction of the calendering is due to the uneven distribution of the oil pits ( ΔRSm/RSm avg ) is used as an indicator. The smaller the ΔRSm/RSm avg , the more uniform the oil sump is distributed on the surface of the copper foil. The reason for dividing by RSm avg is that in the uneven distribution, even if ΔRSm is large, it is not necessarily uneven. In other words, for example, even if ΔRSm is the same, if the RSm avg is large, the distribution unevenness is not large, so the influence is small, and when the RSm avg is small, the distribution unevenness is large and the influence is large.

藉由加快壓延速度，提高壓延油之黏度，或減小每1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1道次之壓下率而易於減少油坑之產生量，且增大RSm。By increasing the calendering speed, increasing the viscosity of the calendering oil, or reducing the reduction ratio per pass, it is easy to increase the amount of crater production and reduce the RSm. 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.

RSm係根據粗糙度曲線與平均線交叉之交點所求得之凹點-週期之間隔的平均值，依據JIS B0601：2001而測定。於本發明中表面粗糙度RSm之平均值(RSmavg )為任意10點之平均值，△RSm係所測定之10點之RSm中，作為最大值之RSmmax 與作為最小值之RSmmin 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10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150mm間隔、較佳為400mm間隔、更佳為1m間隔以上選擇10點。各測定點中之RSm係由對測定點附近測定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。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150mm以上之 測定間隔，則可對該薄片測定表面粗糙度。The RSm is an average value of the pit-period interval obtained from the intersection of the roughness curve and the average line, and is measured in accordance with JIS B0601:2001. In the present invention, the average value (RSm avg ) of the surface roughness RSm is an average value of any 10 points, and the difference between the RSm max which is the maximum value and the RSm min which is the minimum value among the RSm of 10 points measured by the ΔRSm system. . Here, the arbitrary ten points herein do not mean that each of the measurement points is in the vicinity of 10 points. For example, in the case of a coil shape, the length is set to be at least 150 mm intervals in the rolling direction, preferably 400 mm. It is better to select 10 points for the interval of 1 m or more. The RSm in each measurement point was obtained by measuring the average of three times in the vicinity of the measurement point. Furthermore, each measurement point is selected from the RSm in the center in the width direction. Further, in the case where the battery is decomposed, even if a plurality of sheets of the copper foil for negative electrode are stacked, if the measurement interval of 150 mm or more can be secured, the surface roughness can be measured.

於本發明之銅箔的較佳之一實施形態中，△RSm/RSmavg 為0.5以下。In a preferred embodiment of the copper foil of the present invention, ΔRSm/RSm avg is 0.5 or less.

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(tmin )與板厚之平均值(tavg )之差中之任意較大值相對於板厚之平均值(tavg )之比例可設為1.3%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。In a preferred embodiment of the copper foil of the present invention, the difference between the maximum thickness (t max ) of the copper foil and the average value (t avg ) of the sheet thickness, or the minimum value (t min ) and the thickness of the sheet any large difference between the average value (t avg) of the average value of the thickness of (t avg) the ratio can be set to 1.3% or less. The ratio may preferably be 1.2% or less, and more preferably 1.1% or less.

繼而對本發明之銅箔之製造方法進行說明。表面粗糙度Ra之控制可藉由調整工作輥之表面粗糙度而進行，例如若使用Ra大之工作輥則所得壓延銅箔之Ra亦增大，相反若使用Ra小之工作輥則所得壓延銅箔之Ra亦減小。另一方面，通常平均值較大者，不均值本身亦增大。對表面粗糙度Ra之不均值亦相同，表面粗糙度Ra之平均值較大者，不均值亦較大，因此為降低表面粗糙度Ra之不均值，只要減小表面粗糙度Ra之平均值即可。Next, a method of producing the copper foil of the present invention will be described. The control of the surface roughness Ra can be carried out by adjusting the surface roughness of the work roll. For example, if a Ra large work roll is used, the Ra of the obtained rolled copper foil is also increased, and if the Ra small work roll is used, the obtained rolled copper is obtained. The Ra of the foil is also reduced. On the other hand, if the average value is larger, the unevenness itself increases. The unevenness of the surface roughness Ra is also the same, and the average value of the surface roughness Ra is large, and the unevenness value is also large. Therefore, in order to reduce the unevenness of the surface roughness Ra, it is only necessary to reduce the average value of the surface roughness Ra. can.

其中，於各種製品中，有根據與負極活性物質之密合性等觀點而要求之表面粗糙度之要求，因此需要最終製成所要求之值。又，於冷軋中，就可將壓延速度設定成較高之壓延效率之觀點而言，表面粗糙度為某種程度之粗糙較佳。Among them, in various products, there is a demand for surface roughness required from the viewpoint of adhesion to a negative electrode active material, and the like, and it is necessary to finally obtain a desired value. Further, in the cold rolling, the surface roughness is preferably a certain degree of roughness from the viewpoint of setting the rolling speed to a high rolling efficiency.

因此，例如僅最終冷軋之最終道次前之1道次使用表面粗糙度小之工作輥，製作表面粗糙度小即表面平滑之銅箔，於最終道次中使用表面粗糙度大之工作輥，製成所需 之表面粗糙度Ra。Therefore, for example, only one work roll having a small surface roughness is used for one pass before the final pass of the final cold rolling, and a copper foil having a small surface roughness, that is, a smooth surface is produced, and a work roll having a large surface roughness is used in the final pass. Made as needed Surface roughness 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性物質之密合性良好之銅箔。即，至最終道次之2道次前為止利用表面粗糙度Ra粗糙之輥即可，僅最終道次前之1道次，使用較前道次及最終道次粗糙度更小之輥。Thereby, a copper foil having a high thickness precision and having a desired surface roughness and having good adhesion to an active material can be obtained. That is, it is sufficient to use a roll having a rough surface roughness Ra up to two passes before the final pass, and to use a roll having a smaller roughness than the previous pass and the final pass only one pass before the final pass.

不僅最終道次前之1道次，其之前之道次亦可使用表面粗糙度小之工作輥，但表面粗糙度小之輥無法提高壓延速度，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，若忽視生產性之觀點，則最終道次前1道次更之前的道次亦使用表面粗糙度小之輥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道次使用表面粗糙度小之輥亦有效果。Not only the first pass before the final pass, but also the work roll having a small surface roughness can be used in the previous pass, but the roll having a small surface roughness cannot increase the rolling speed, and thus it is not preferable from the viewpoint of productivity. Therefore, it is generally only necessary to reduce the surface roughness of the work rolls used in the pass before the final pass. Among them, if the viewpoint of productivity is neglected, the effect of reducing the unevenness of the surface roughness is also high by using a roller having a small surface roughness in the previous pass of the last pass. For example, it is effective to use a roller having a small surface roughness only for the second pass before the final pass.

於最終道次中，工作輥使用表面粗糙度Ra超過0.01μm者以使銅箔之壓延平行方向之Ra之平均值(Raavg )為0.01~0.15μm，因此為減小表面粗糙度之不均值，最終道次前之1道次所使用之工作輥之表面粗糙度Ra必需比於最終道次所使用之工作輥更小。因此，最終道次前之1道次所使用之工作輥之表面粗糙度Ra較理想為0.01μm以下。In the final pass, the work roll has a surface roughness Ra of more than 0.01 μm so that the average value (Ra avg ) of Ra in the parallel direction of the copper foil is 0.01 to 0.15 μm, so that the unevenness of the surface roughness is reduced. The surface roughness Ra of the work rolls used in the first pass before the final pass must be smaller than the work rolls used in the final pass. Therefore, the surface roughness Ra of the work rolls used in the first pass before the final pass is preferably 0.01 μm or less.

然而，穩定製作表面粗糙度Ra為0.01μm以下且無表面損傷等之外觀上的問題之輥，需要較高的技術，且於花費方面亦相對地變高。However, a roller which stably produces a surface roughness Ra of 0.01 μm or less and has no external appearance such as surface damage requires a high technique and is relatively expensive in terms of cost.

因此，更佳的範圍係於最終道次中所使用的工作輥其表面粗糙度Ra為0.03μm以上為較佳，因此，使用於最終道次前1個道次之工作輥的表面粗糙度Ra較佳為未達0.03μm。Therefore, a more preferable range is preferable that the work roll used in the final pass has a surface roughness Ra of 0.03 μm or more, and therefore, the surface roughness Ra of the work roll used in the first pass of the final pass is used. It is preferably less than 0.03 μm.

為降低表面粗糙度RSm之不均，使油坑之分佈均勻變得重要。為使油坑之分佈均勻，在若干之因素中將壓延油之黏度於壓延過程中保持固定亦為重要。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緩升溫從而使黏度降低。若伴隨壓延油之黏度之變化，壓延油壓入銅箔表面之程度發生變化，則導致油坑分佈之不均。In order to reduce the unevenness of the surface roughness RSm, it is important to make the distribution of the oil pit uniform. In order to make the distribution of the oil pit uniform, it is also important to keep the viscosity of the rolling oil constant during the calendering process among several factors. The viscosity of the rolling oil is basically determined according to the type of the rolling oil, and the rolling oil is gradually heated due to the processing heat in the rolling process to lower the viscosity. If the degree of change of the viscosity of the rolling oil into the surface of the copper foil changes with the change in the viscosity of the rolling oil, uneven distribution of the oil pit is caused.

例如壓延油於壓延前之溫度調整時保持在25℃左右時，若將壓延油噴射至壓延過程中之工作輥則由因加工熱而升溫之工作輥等之熱量會傳導，壓延油升溫至40℃左右。若可維持在該狀態，則油坑之分佈之不均少，對銅箔形狀不會產生問題。然而，於壓延油之溫度控制不充分，壓延油溫度超過40℃而發生不均之情形時，不僅銅箔之表面性狀容易發生不均，亦會對板形狀造成影響。因此，為將壓延過程中之壓延油之溫度調整至40℃左右，必需綜合性調整輥噴射前之壓延油溫度、壓延速度、加工度等。For example, when the rolling oil is maintained at about 25 ° C during the temperature adjustment before rolling, if the rolling oil is sprayed to the work roll in the rolling process, the heat of the work roll heated by the processing heat is conducted, and the rolling oil is heated to 40. °C or so. If this state can be maintained, the unevenness of the distribution of the oil pits is small, and there is no problem in the shape of the copper foil. However, when the temperature control of the rolling oil is insufficient and the rolling oil temperature exceeds 40 ° C and unevenness occurs, not only the surface properties of the copper foil tend to be uneven, but also the shape of the sheet. Therefore, in order to adjust the temperature of the rolling oil in the rolling process to about 40 ° C, it is necessary to comprehensively adjust the rolling oil temperature, the rolling speed, the degree of work, and the like before the roll injection.

可使用藉由以本發明之壓延銅箔為材料之集電器及形成於其上之活性物質所構成之負極，並利用慣用方法來製作鋰離子電池。於鋰離子電池中，包含電解質中之鋰離子負責導電之鋰離子一次電池及鋰離子二次電池。負極活性物質，並無限制，可列舉：碳、矽、錫、鍺、鉛、銻、鋁、銦、鋰、氧化錫、鈦酸鋰、氮化鋰、將銦固溶之氧化錫、銦-錫合金、鋰-鋁合金、鋰-銦合金等。A lithium ion battery can be produced by a conventional method using a negative electrode comprising a current collector made of the rolled copper foil of the present invention and an active material formed thereon. In a lithium ion battery, a lithium ion primary battery and a lithium ion secondary battery in which lithium ions in an electrolyte are responsible for conduction are included. The negative electrode active material is not limited, and examples thereof include carbon, antimony, tin, antimony, lead, antimony, aluminum, indium, lithium, tin oxide, lithium titanate, lithium nitride, tin oxide, indium in which indium is dissolved. Tin alloy, lithium-aluminum alloy, lithium-indium alloy, and the like.

[實施例][Examples]

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。The embodiments of the present invention are shown below, but are provided to provide a better understanding of the present invention and are not intended to limit the invention.

＜例1(表面粗糙度Ra之不均之影響)＞<Example 1 (Impact of unevenness of surface roughness Ra)>

[壓延銅箔之製造][Manufacture of rolled copper foil]

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10m以上且設定厚度10μm之壓延銅箔(No.1～6)。於最終冷軋中，僅於最終道次前1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1。所使用之壓延油之黏度為7.0cSt(40℃)，最終冷軋中之壓延油之溫度控制在40℃左右。工作輥之表面粗糙度依據JIS B0601：2001，以接觸式之表面粗糙度計進行測定。After the ingot of the refined copper is hot-rolled, it is subjected to reverse annealing and cold rolling, and finally cold-rolled to obtain a rolled copper foil (No. 1 to 6) having a length of 10 m or more and a thickness of 10 μm in the rolling direction. In the final cold rolling, the surface roughness of the work rolls used only once before the final pass, and the surface roughness of the work rolls used in the final pass are shown in Table 1. The viscosity of the calendered oil used was 7.0 cSt (40 ° C), and the temperature of the calendered oil in the final cold rolling was controlled at about 40 ° C. The surface roughness of the work rolls was measured in accordance with JIS B0601:2001 using a contact surface roughness meter.

將所獲得之壓延銅箔放置並固定於玻璃板上，使用Lasertec公司之共軛焦顯微鏡(confocol microscope)HD100D，基於上述測定方法算出Raavg 、ΔRa、RSmavg 、及ΔRSm。結果示於表1。The obtained rolled copper foil was placed and fixed on a glass plate, and Ra avg , ΔRa, RSm avg , and ΔRSm were calculated based on the above-described measurement method using a condensed focal microscope HD100D of Lasertec. The results are shown in Table 1.

[板厚精度評價][Plate thickness accuracy evaluation]

壓延銅箔之板厚依據重量法(IPC-TM-650)進行測定。自所獲得之銅箔選擇任意之10m之壓延方向長度，對此以1m間隔測定10點板厚。各測定點之板厚T採取3次測定之平均值。將10點之T之平均值設為Tavg 、10點之T之最大值設為Tmax 、10點之T之最小值設為Tmin 。於表1中將(Tavg -Tmin )/Tavg 及(Tmax -Tavg )/Tavg 之較大者記述為「板厚不均(%)」。The thickness of the rolled copper foil was measured by a gravimetric method (IPC-TM-650). From the obtained copper foil, an arbitrary length of 10 m in the rolling direction was selected, and 10 points of sheet thickness was measured at intervals of 1 m. The plate thickness T of each measurement point was averaged three times. The average value of T at 10 o'clock is T avg , the maximum value of T at 10 o'clock is T max , and the minimum value of T at 10 o'clock is T min . In Table 1, the larger of (T avg - T min ) / T avg and (T max - T avg ) / T avg is described as "thickness unevenness (%)".

No.1～No.4為發明例，能夠將板厚之不均抑制為1.3%以下。No. 1 to No. 4 are examples of the invention, and the unevenness of the sheet thickness can be suppressed to 1.3% or less.

No.5係最終道次前之1道次之表面粗糙度大，因此無法充分控制ΔRa。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糙度，但依然無法充分控制ΔRa。No. 5 is one step before the final pass, and the surface roughness is large, so ΔRa cannot be sufficiently 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 ΔRa was not sufficiently controlled.

＜例2(油坑之分佈之影響)＞<Example 2 (Impact of the distribution of oil pits)>

[壓延銅箔之製造][Manufacture of rolled copper foil]

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10m以上且設定厚度10μm之壓延銅箔(No.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0.010μm，及將最終道次所使用之工作輥表面粗糙度Ra設為0.050μm。所使用之壓延油之黏度為7.0cSt(40℃)，發明例係將最終冷軋中之壓延油之溫度調整為40℃左右。各種特性評價以與例1相同之方法進行。試驗結果示於表2。After the ingot of the refined copper is hot-rolled, it is subjected to reverse annealing and cold rolling, and finally cold-rolled, and a rolled copper foil (No. 7 to 12) having a length of 10 m or more and a thickness of 10 μm in the rolling direction is obtained. In the final cold rolling, the work roll surface roughness Ra used until the final pass was set to 0.010 μm, and the work roll surface roughness Ra used in the final pass was set to 0.050 μm. The viscosity of the calendering oil used was 7.0 cSt (40 ° C), and in the invention, the temperature of the rolling oil in the final cold rolling was adjusted to about 40 °C. Various characteristic evaluations were carried out in the same manner as in Example 1. The test results are shown in Table 2.

發明例No.7～9係將最終壓延機之壓延油之溫度管理管理為40℃，因此油坑之分佈均勻、不均較少、板厚之不均為小至未達1.2%。In the invention examples No. 7 to 9, the temperature management of the rolling oil of the final calender was 40 ° C, so that the distribution of the oil pits was uniform, the unevenness was small, and the thickness of the plate thickness was as small as less than 1.2%.

發明例No.10～12中，除最終冷軋機中之壓延油之溫度管理以外，以與發明例No.7～9相同之條件來實施。此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℃升溫至45℃左右。雖於測定時未能確認，但推測亦有局部超過50℃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1.2%之實例。In the invention examples Nos. 10 to 12, the same conditions as in the inventive examples Nos. 7 to 9 were carried out except for the temperature management of the rolling oil in the final cold rolling mill. Since the management of the temperature of the rolling oil in the final cold rolling mill is not sufficiently performed here, the temperature is raised to about 45 ° C over 40 ° C. Although it was not confirmed at the time of measurement, it was presumed that there was 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 1.2%.

Claims (8)

一種鋰離子電池集電器用銅箔，其壓延平行方向之表面粗糙度Ra之任意10點之平均值(Raavg )為0.01~0.15μm，△Ra=Ramax -Ramin 為0.025μm以下，銅箔之板厚為5~20μm。A copper foil for a lithium ion battery current collector, wherein an average value (Ra avg ) of any 10 points of the surface roughness Ra in the parallel direction of rolling is 0.01 to 0.15 μm, and ΔRa = Ra max - Ra min is 0.025 μm or less, copper The foil has a plate thickness of 5 to 20 μm. 如申請專利範圍第1項之鋰離子電池集電器用銅箔，其中，銅箔之板厚之最大值(tmax )與板厚之平均值(tavg )之差，或板厚之最小值(tmin )與板厚之平均值(tavg )之差中之任意較大值相對於板厚之平均值(tavg )之比例為1.3%以下。The copper foil for a lithium ion battery current collector according to the first aspect of the patent application, wherein the difference between the maximum thickness (t max ) of the copper foil and the average value (t avg ) of the thickness, or the minimum thickness the proportion of any larger value of the difference (t min) and the average value (t avg) of the thickness of the sheet thickness relative to the average of (t avg) is 1.3% or less. 如申請專利範圍第1項之鋰離子電池集電器用銅箔，其中，△RSm=RSmmax -RSmmin 對於壓延平行方向之表面粗糙度RSm之任意10點之平均值(RSmavg )之比(△RSm/RSmavg )為0.5以下。The copper foil for a lithium ion battery current collector according to the first aspect of the invention, wherein ΔRSm=RSm max −RSm min is a ratio of an average value (RSm avg ) of any 10 points of the surface roughness RSm in the parallel direction of rolling ( ΔRSm/RSm avg ) is 0.5 or less. 如申請專利範圍第1項之鋰離子電池集電器用銅箔，其係鋰離子二次電池負極集電器用。 For example, the copper foil for a lithium ion battery current collector of the first application of the patent scope is used for a lithium ion secondary battery anode current collector. 如申請專利範圍第2項之鋰離子電池集電器用銅箔，其係鋰離子二次電池負極集電器用。 For example, the copper foil for a lithium ion battery current collector of the second aspect of the patent application is used for a lithium ion secondary battery anode current collector. 如申請專利範圍第3項之鋰離子電池集電器用銅箔，其係鋰離子二次電池負極集電器用。 For example, the copper foil for a lithium ion battery current collector of the third aspect of the patent application is used for a lithium ion secondary battery anode current collector. 一種鋰離子電池，其具備申請專利範圍第1至6項中任一項之銅箔作為集電器。 A lithium ion battery comprising the copper foil according to any one of claims 1 to 6 as a current collector. 一種鋰離子電池集電器用銅箔之製造方法，其係於最終冷軋步驟中，用於最終道次之工作輥之表面粗糙度Ra為 0.03μm以上，用於最終道次前1道次之工作輥之表面粗糙度Ra未達0.03μm。 A method for producing a copper foil for a lithium ion battery current collector, which is used in the final cold rolling step, and the surface roughness Ra of the work roll for the final pass is Above 0.03 μm, the surface roughness Ra of the work rolls for the first pass of the final pass is less than 0.03 μm.
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