TWI639731B - Electrolytic copper foil and method for producing the same, and current collector for lithium secondary battery and secondary battery comprising the electrolytic copper foil - Google Patents
Electrolytic copper foil and method for producing the same, and current collector for lithium secondary battery and secondary battery comprising the electrolytic copper foil Download PDFInfo
- Publication number
- TWI639731B TWI639731B TW104118592A TW104118592A TWI639731B TW I639731 B TWI639731 B TW I639731B TW 104118592 A TW104118592 A TW 104118592A TW 104118592 A TW104118592 A TW 104118592A TW I639731 B TWI639731 B TW I639731B
- Authority
- TW
- Taiwan
- Prior art keywords
- copper foil
- electrolytic copper
- fracture
- point
- time
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
根據本發明之一示範性具體實施例之電解銅箔係符合於當作鋰二次電池的一集流體使用的電解銅箔，且當在190℃退火達1小時，該電解銅箔具有介於5.0和18.0間範圍的斷裂模數特徵(f)，其中該斷裂模數特徵(f)是定義為f＝{(C－B)/A}×1000，其中A表示當該電解銅箔的斷裂在該電解銅箔的拉伸測試開始時的時間點處的該電解銅箔的應力；B表示當該電解銅箔的斷裂開始時的時間點處的延伸；C表示當該電解銅箔的斷裂結束時的時間點處的延伸，當該電解銅箔的斷裂開始時的該時間點係對應於當該隨著逐漸增加延伸而增加的應力開始在拉伸測試中減少時的一時間點，且當該電解銅箔的斷裂結束時的該時間點係對應於當該電解銅箔斷裂且分成兩或多個片段時的一時間點。An electrolytic copper foil according to an exemplary embodiment of the present invention conforms to an electrolytic copper foil used as a current collector of a lithium secondary battery, and when annealed at 190 ° C for 1 hour, the electrolytic copper foil has a The modulus of rupture characteristic (f) in the range between 5.0 and 18.0, wherein the modulus of rupture (f) is defined as f = {(C - B) / A} × 1000, where A represents the fracture of the electrolytic copper foil The stress of the electrolytic copper foil at the time point when the tensile test of the electrolytic copper foil is started; B represents the elongation at the time when the fracture of the electrolytic copper foil starts; and C represents the fracture of the electrolytic copper foil. The extension at the time point at the end, the time point when the fracture of the electrolytic copper foil starts is a point in time when the stress which increases as the gradually increasing extension starts to decrease in the tensile test, and This point in time when the rupture of the electrolytic copper foil ends corresponds to a point in time when the electrolytic copper foil is broken and divided into two or more segments.
Description
本發明有關電解銅箔與一種用於製造該電解銅箔的方法、及用於鋰二次電池的集流體、以及含有該電解銅箔的二次電池；更具體地，有關具有受限於預定範圍的斷裂模數特徵以改善二次電池特徵的電解銅箔；一種用於產生電解銅箔的方法；以及用於鋰二次電池的集流體及含有該電解銅箔的鋰二次電池。 The present invention relates to an electrolytic copper foil, a method for producing the electrolytic copper foil, a current collector for a lithium secondary battery, and a secondary battery including the electrolytic copper foil; more specifically, the related one is limited by the schedule An electrolytic copper foil characterized by a rupture modulus characteristic of the range to improve secondary battery characteristics; a method for producing an electrolytic copper foil; and a current collector for a lithium secondary battery and a lithium secondary battery containing the electrolytic copper foil.
本專利申請主張2014年7月10日在韓國申請的韓國專利申請案第10-2014-0086970號的優先權，其內容在此併入本文供參考。 The present application claims priority to Korean Patent Application No. 10-2014-0086970, filed on Jan. 10, 2014, the entire disclosure of which is hereby incorporated by reference.
相較於其他二次電池，由於具備諸如較高能量密度、較高工作電壓和較佳保存和壽命特徵的優點，使得鋰二次電池廣泛使用在各種不同類型電子裝置，包括個人電腦、手提攝影機、行動電話、可攜式可攜式CD播放機、與個人數位助理(PDA，Personal Digital Assistant)。 Compared with other secondary batteries, lithium secondary batteries are widely used in various types of electronic devices, including personal computers and hand-held cameras, due to advantages such as higher energy density, higher operating voltage, and better preservation and life characteristics. , mobile phone, portable CD player, and personal digital assistant (PDA, Personal Digital Assistant).
通常，鋰二次電池包括一正電極與一負電極，其間存在電解質，該正電極的一正電極主動材料黏合一正電極集流體，且該負電極的一負電極主動材料黏合一負電極集流體。 Generally, a lithium secondary battery includes a positive electrode and a negative electrode with an electrolyte therebetween, a positive electrode active material of the positive electrode is bonded to a positive electrode current collector, and a negative electrode active material of the negative electrode is bonded to a negative electrode set. fluid.
在鋰二次電池，負電極集流體主要是利用一電解銅箔製成，且電解銅箔需要有良好特性，以當對二次電池進行充電及放電時，在二次電池內的重複嚴苛情況之下維持二次電池性能。 In a lithium secondary battery, the negative electrode current collector is mainly made of an electrolytic copper foil, and the electrolytic copper foil needs to have good characteristics, so that when the secondary battery is charged and discharged, the repetition in the secondary battery is severe. Maintain secondary battery performance under conditions.
電解銅箔所需的特性可(例如)包括下列特性：在充電與放電期間的重複嚴苛情況之下避免裂開產生；當充電與放電持續時，抑制放電容量維持率的加速衰減速度；及免除由於內部過熱及/或意外事件風險所引起二次電池性能衰減。 The characteristics required for the electrolytic copper foil may, for example, include the following characteristics: avoiding cracking generation under repeated severe conditions during charging and discharging; and suppressing accelerated decay rate of discharge capacity retention rate when charging and discharging are continued; Eliminates secondary battery performance degradation due to internal overheating and/or risk of accidents.
電解銅箔可藉由控制各種不同因素而有良好特性，但非常不容易發現應控制哪些因素以獲得想要的特性與應進行控制的範圍。 Electrolytic copper foil can have good characteristics by controlling various factors, but it is very difficult to find out which factors should be controlled to obtain the desired characteristics and the range to be controlled.
本發明是針對解決前述問題而設計，因此，本發明藉由發現及控制用以確保鋰二次電池的良好效能的重要因素，針對良好性能的鋰二次電池提供具適當特性的電解銅箔。 The present invention has been devised in order to solve the aforementioned problems. Therefore, the present invention provides an electrolytic copper foil having appropriate characteristics for a lithium secondary battery having good performance by discovering and controlling an important factor for ensuring good performance of a lithium secondary battery.
本發明的其他目的和優點可從本發明的下列描述和示範性具體實施例變得更明白。同時，應瞭解，本發明的目的和優點可利用文後申請專利範圍說明的構件和組合加以實現。 Other objects and advantages of the present invention will become apparent from the following description and exemplary embodiments. In the meantime, it is to be understood that the objects and advantages of the present invention can be realized by the elements and combinations described in the appended claims.
為了達成前述目的，發明家已重複研究和實驗，因此，他們發現，當具適當受控斷裂模數特徵的電解銅箔當作鋰二次電池的集流體使用時，儘管重複充電和放電，鋰二次電池可較佳維持其特徵。 In order to achieve the foregoing objectives, the inventors have repeated research and experiments. Therefore, they have found that when an electrolytic copper foil having a suitably controlled modulus of rupture is used as a current collector of a lithium secondary battery, lithium is repeatedly charged and discharged despite repeated charging and discharging. The secondary battery can preferably maintain its characteristics.
同樣地，根據本發明之一示範性具體實施例之可較佳維持鋰二次電池特徵之電解銅箔係符合於當作鋰二次電池的集流體使用的電解銅箔，且當在190℃退火達1小時，電解銅箔具有介於5.0和 18.0間範圍的斷裂模數特徵(f)。 Similarly, an electrolytic copper foil which can preferably maintain the characteristics of a lithium secondary battery according to an exemplary embodiment of the present invention conforms to an electrolytic copper foil used as a current collector of a lithium secondary battery, and when it is at 190 ° C Annealed for 1 hour, electrolytic copper foil has between 5.0 and Fracture modulus characteristics (f) in the range of 18.0.
在本說明書，斷裂模數特徵(f)是定義為f={(C-B)/A}×1000，其中A表示當該電解銅箔的斷裂在該電解銅箔的拉伸測試開始時的時間點處的該電解銅箔的應力；B表示當該電解銅箔的斷裂開始時的時間點處的延伸；C表示當該電解銅箔的斷裂結束時的時間點處的延伸，當該電解銅箔的斷裂開始時的該時間點係對應於當該隨著逐漸增加延伸而增加的應力開始在拉伸測試中減少時的一時間點，且當該電解銅箔的斷裂結束時的該時間點係對應於當該電解銅箔斷裂且分成兩或多個片段時的一時間點。 In the present specification, the modulus of rupture (f) is defined as f = {(CB) / A} × 1000, where A represents the time when the fracture of the electrolytic copper foil is at the beginning of the tensile test of the electrolytic copper foil. The stress of the electrolytic copper foil at the point; B represents the elongation at the time when the fracture of the electrolytic copper foil starts; C represents the elongation at the time when the fracture of the electrolytic copper foil is finished, when the electrolytic copper foil The point in time at which the fracture starts is a point in time when the stress which increases as the elongation increases gradually starts to decrease in the tensile test, and the time point when the fracture of the electrolytic copper foil ends Corresponding to a point in time when the electrolytic copper foil is broken and divided into two or more segments.
該電解銅箔具有形成於表面的一保護層，且該保護層可利用從鉻酸鹽、苯並三氮唑(BTA)、和矽烷偶聯劑選取的至少一者製成。 The electrolytic copper foil has a protective layer formed on the surface, and the protective layer can be made of at least one selected from chromate, benzotriazole (BTA), and a decane coupling agent.
該電解銅箔可有小於20μm(微米)的厚度。 The electrolytic copper foil may have a thickness of less than 20 μm (micrometers).
該電解銅箔可有超過0且小於或等於2μm(微米)的表面粗糙度(Rz)。 The electrolytic copper foil may have a surface roughness (Rz) of more than 0 and less than or equal to 2 μm (micrometers).
該電解銅箔可藉由用於產生根據本發明之一示範性具體實施例之電解銅箔的方法而產生，且當在190℃退火達1小時，用於產生根據本發明之一示範性具體實施例之電解銅箔的方法係符合產生具有介於5.0和18.0間範圍斷裂模數特徵(f)的電解銅箔的方法，且包括(a)備製硫酸銅的水溶液，其具有介於70g/L(公克/公升)和80g/L(公克/公升)間的銅濃度、及介於80g/L(公克/公升)和110g/L(公克/公升)間的 硫酸濃度；及(b)在介於40℃和45℃間的溫度和介於40A/m2(每平方公尺安培數)和70A/m2(每平方公尺安培數)間的電流密度，將硫酸銅的水溶液當作電解液使用，使銅(Cu)電沉積在電解機的鼓面。 The electrolytic copper foil can be produced by a method for producing an electrolytic copper foil according to an exemplary embodiment of the present invention, and when annealed at 190 ° C for 1 hour, for producing an exemplary specific one according to the present invention The method of electrolytic copper foil of the embodiment is in accordance with a method of producing an electrolytic copper foil having a modulus of rupture (f) ranging between 5.0 and 18.0, and comprising (a) an aqueous solution of copper sulfate prepared having a ratio of 70 g. Copper concentration between /L (g/L) and 80g/L (g/L), and between 80g/L (g/L) and 110g/L (g/L) Sulfuric acid concentration; and (b) current density between 40 ° C and 45 ° C and current density between 40 A / m 2 (amperes per square meter) and 70 A / m 2 (amperes per square meter) An aqueous solution of copper sulfate was used as an electrolyte to deposit copper (Cu) on the drum surface of the electrolysis machine.
該方法可包括(c)形成一保護層在該電沉積銅層的表面，該保護層可利用從鉻酸鹽、苯並三氮唑(BTA)、和矽烷偶聯劑選取的至少一者製成。 The method may comprise (c) forming a protective layer on the surface of the electrodeposited copper layer, the protective layer being at least one selected from the group consisting of chromate, benzotriazole (BTA), and a decane coupling agent. to make.
同時，前述目的可藉由用於從該電解銅箔製成的鋰二次電池之電極集流體、及包含用於鋰二次電池的電極集流體之鋰二次電池加以達成。 Meanwhile, the foregoing object can be attained by an electrode current collector for a lithium secondary battery made of the electrolytic copper foil, and a lithium secondary battery including an electrode current collector for a lithium secondary battery.
根據本發明，在二次電池的充電和放電所造成鋰二次電池內的重複嚴苛情況之下，能夠降低減少鋰二次電池的容量維持率及/或避免發生內部過熱引起的火災，藉此改善二次電池的效能及/或確保二次電池使用時的安全性。 According to the present invention, under the severe severe conditions in the lithium secondary battery caused by the charging and discharging of the secondary battery, it is possible to reduce the capacity retention rate of the lithium secondary battery and/or to avoid a fire caused by internal overheating, This improves the performance of the secondary battery and/or ensures the safety when the secondary battery is used.
10‧‧‧電解銅箔 10‧‧‧electrolytic copper foil
11‧‧‧銅層 11‧‧‧ copper layer
11a‧‧‧光澤面 11a‧‧‧Glossy face
11b‧‧‧去光澤面 11b‧‧‧Glossy face
12‧‧‧保護層 12‧‧‧Protective layer
附圖示意說明本發明連同前面揭露的一較佳具體實施例，用來提供對本發明之技術精神的進一步理解，因此，本發明未構成受限於附圖。 BRIEF DESCRIPTION OF THE DRAWINGS The present invention, together with a preferred embodiment of the present invention, is provided to provide a further understanding of the technical spirit of the present invention, and thus the present invention is not limited by the accompanying drawings.
圖1為示意說明根據本發明之一示範性具體實施例之電解銅箔的截面圖。 1 is a cross-sectional view schematically illustrating an electrolytic copper foil in accordance with an exemplary embodiment of the present invention.
圖2為示意說明在電解銅箔拉伸測試期間的電解銅箔斷裂之製程的圖式。 Fig. 2 is a view schematically showing a process for breaking an electrolytic copper foil during an electrolytic copper foil tensile test.
圖3為示意說明斷裂模數特徵的應力和延伸關係圖。 Figure 3 is a graph showing stress and elongation relationships illustrating the modulus of rupture.
以下，本發明的較佳具體實施例將參考附圖詳細描述。描述以前，應瞭解，本說明書和文後申請專利範圍中使用的術語應不構成侷限於一般和字典意義，而是根據允許發明家適當定義最佳解釋術語的原則，基於符合本發明的技術態樣的意義和觀念來解釋。因此， 在本說明書提議的描述只是為了示意說明的較佳實例，而不是要限制本發明的範疇；因此，應瞭解，其他同等物和修改是可能的，不致悖離本發明的精神與範疇。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Before the description, it should be understood that the terms used in the specification and the scope of the patent application should not be construed as being limited to the general and dictionary sense, but based on the principle that the inventor is allowed to appropriately define the best interpretation term, based on the technical aspect consistent with the present invention. The meaning and concept of the explanation. therefore, The descriptions of the present invention are intended to be illustrative only and not to limit the scope of the present invention; therefore, it is understood that other equivalents and modifications are possible without departing from the spirit and scope of the invention.
根據本發明之一示範性具體實施例之電解銅箔(10)將參考圖1描述。 An electrolytic copper foil (10) according to an exemplary embodiment of the present invention will be described with reference to FIG.
圖1為示意說明根據本發明之一示範性具體實施例之電解銅箔的截面圖。 1 is a cross-sectional view schematically illustrating an electrolytic copper foil in accordance with an exemplary embodiment of the present invention.
請即參考圖1，根據本發明之一示範性具體實施例之電解銅箔(10)包括一銅層(11)；及一保護層(12)，其為選擇性形成於銅層(11)的表面。 Referring to FIG. 1, an electrolytic copper foil (10) according to an exemplary embodiment of the present invention includes a copper layer (11); and a protective layer (12) selectively formed on the copper layer (11). s surface.
電解銅箔(10)最好當作鋰二次電池的一負電極集流體使用。即是，在鋰二次電池，最好將電解銅箔(10)當作黏結負電極主動材料的一負電極集流體使用。一般是採用鋁(Al)製成的箔，當作黏結正電極主動材料的一正電極集流體。 The electrolytic copper foil (10) is preferably used as a negative electrode current collector of a lithium secondary battery. That is, in the lithium secondary battery, it is preferable to use the electrolytic copper foil (10) as a negative electrode current collector for bonding the active material of the negative electrode. A foil made of aluminum (Al) is generally used as a positive electrode current collector for bonding the active material of the positive electrode.
因此，本發明係採用一實例來描述，該案例在於使用根據本發明之一示範性具體實施例之電解銅箔(10)的二次電池之集流體係對應於一負電極集流體。 Accordingly, the present invention is described by way of an example in which a current collecting system using a secondary battery of an electrolytic copper foil (10) according to an exemplary embodiment of the present invention corresponds to a negative electrode current collector.
當作為鋰二次電池的集流體使用時，電解銅箔(10)會由於來自重複充電與放電造成電極體積膨脹而受力，且在此情況，即使施加的張力強度大於電解銅箔(10)的斷裂強度，確實會立即發生斷裂。 When used as a current collector of a lithium secondary battery, the electrolytic copper foil (10) is subjected to force due to expansion of the electrode volume due to repeated charging and discharging, and in this case, even if the applied tensile strength is greater than that of the electrolytic copper foil (10) The breaking strength does break immediately.
即是，請即參考圖2，電解銅箔(10)在該表面上面透過一頸縮步驟、一空隙產生步驟、一空隙生長和接合步驟、與一剪切發生步驟而達到完全斷裂。 That is, referring to Fig. 2, the electrolytic copper foil (10) is completely broken on the surface by a necking step, a void generating step, a gap growing and joining step, and a shear generating step.
此斷裂的形式稱為延展性斷裂，且請即參考圖3，在代表延展性斷裂的應力和延伸關係圖中，電解銅箔(10)呈現在電解銅箔的 應力到達斷裂強度之後，隨著逐漸增加延伸而逐漸減少應力的趨勢，且最終，電解銅箔(10)到達完全斷裂。 The form of this fracture is called ductile fracture, and please refer to FIG. 3, in the stress and elongation diagram representing the ductile fracture, the electrolytic copper foil (10) is present in the electrolytic copper foil. After the stress reaches the breaking strength, the tendency of the stress is gradually reduced as the elongation is gradually increased, and finally, the electrolytic copper foil (10) reaches a complete fracture.
在將從應力到達斷裂強度的時間點處至電解銅箔(10)到達完全斷裂的時間點處的延伸變化除以在斷裂開始處的一應力值之後，即是一斷裂強度值，藉由將結果乘以1000所獲得的值稱為一斷裂模數特徵(f)。 After the change from the point at which the stress reaches the breaking strength to the point at which the electrolytic copper foil (10) reaches the complete fracture is divided by the value of the stress at the beginning of the fracture, it is a value of the breaking strength, The result obtained by multiplying the result by 1000 is called a modulus of rupture (f).
請即參考圖3，斷裂模數特徵(f)可採用下列方程式表示：F={(C-B)/A}×1000 Referring to Figure 3, the modulus of rupture (f) can be expressed by the following equation: F = {(C-B) / A} × 1000
其中，在電解銅箔的拉伸測試中，A表示當電解銅箔的斷裂開始時的時間點處的電解銅箔的應力；B表示當電解銅箔的斷裂開始時的時間點處的延伸；及C表示當電解銅箔的斷裂結束時的時間點處的延伸。 Wherein, in the tensile test of the electrolytic copper foil, A represents the stress of the electrolytic copper foil at the time point when the fracture of the electrolytic copper foil starts; and B represents the elongation at the time point when the fracture of the electrolytic copper foil starts; And C represents the elongation at the time point when the fracture of the electrolytic copper foil ends.
在圖3的壓力與延伸關係圖中，當電解銅箔的斷裂開始時的時間點係代表對應於隨著逐漸增加延伸而逐漸增加的應力開始減少之一點P1處的時間。 In the pressure and extension diagram of Fig. 3, the time point when the fracture of the electrolytic copper foil starts is a time at which the point P1 corresponding to the stress which gradually increases as the gradually increasing extension starts to decrease.
同時，在圖3的壓力與延伸關係圖中，當電解銅箔的斷裂結束時的時間點係代表對應於隨著逐漸增加延伸而逐漸減少的應力變成零之一點P2處的時間，且在此時間點，電解銅箔斷裂且分成兩或多片段。 Meanwhile, in the pressure and extension relationship diagram of FIG. 3, the time point when the fracture of the electrolytic copper foil ends is a time corresponding to a point P2 at which the stress gradually decreased as the gradually increasing extension becomes zero, and is here. At the time point, the electrolytic copper foil is broken and divided into two or more segments.
在斷裂模數特徵(f)具有太小值的情況，當電解銅箔(10)受到外力而裂開時，電解銅箔(10)會在短時間內裂開，因此，當電解銅箔(10)當作鋰二次電池的一集流體使用時，二次電池在從重複充電與放電的造成二次電池的嚴苛內部狀況之下不容易維持效能。 In the case where the rupture modulus characteristic (f) has a too small value, when the electrolytic copper foil (10) is cracked by an external force, the electrolytic copper foil (10) is cracked in a short time, and therefore, when the electrolytic copper foil ( 10) When used as a current collector of a lithium secondary battery, the secondary battery does not easily maintain its efficiency under the severe internal conditions of the secondary battery caused by repeated charging and discharging.
對照下，在斷裂模數特徵(f)具有太大值的情況，不穩定 狀態在電解銅箔(10)受到外力而裂開的情況會持續較久，且可能發生過熱產生，因此，會有電池效能惡化的問題且無法確保二次電池使用時的安全性。 In contrast, in the case where the modulus of rupture (f) has a large value, it is unstable. The state in which the electrolytic copper foil (10) is cracked by an external force continues for a long time, and overheating may occur, so that there is a problem that the battery performance is deteriorated and the safety of the secondary battery cannot be ensured.
因此，斷裂模數特徵(f)需要維持適當的範圍，最好介於5.0和18.0間範圍。 Therefore, the modulus of rupture (f) needs to be maintained in an appropriate range, preferably in the range between 5.0 and 18.0.
斷裂模數特徵(f)是在電解銅箔(10)在190℃退火達1小時之此一狀態中測量，且執行退火，以在鋰二次電池的製造中施加高溫度情況，其將電解銅箔(10)當作一集流體使用。 The modulus of rupture (f) is measured in a state in which the electrolytic copper foil (10) is annealed at 190 ° C for 1 hour, and annealing is performed to apply a high temperature condition in the manufacture of the lithium secondary battery, which will electrolyze Copper foil (10) is used as a current collector.
斷裂模數特徵(f)可透過下列的變化而受控制：改變在電解銅箔(10)的製造中供電鍍的電鍍液(電解液)中的銅和 硫酸濃度、改變選擇性添加於電鍍液的各種不同類型添加劑(無機添加劑、均勻劑、增亮劑)的濃度、改變電鍍時的電流密度、及改變電鍍液的溫度。 The modulus of rupture (f) can be controlled by changing the copper and the plating solution (electrolyte) in the supply of electrolytic copper foil (10). The concentration of sulfuric acid changes the concentration of various types of additives (inorganic additives, homogenizers, brighteners) selectively added to the plating solution, changes the current density during plating, and changes the temperature of the plating solution.
在此例證中，利用電渡製成的電解銅箔(10)包括一光澤面(11a)，其具有一低表面粗糙度(Rz)；及一去光澤面(11b)，其表面係相反於該光澤面(11a)，且具有呈現所謂山輪廓結構的較高表面粗糙度(Rz)。 In this illustration, an electrolytic copper foil (10) made by using an electric ferrite includes a glossy surface (11a) having a low surface roughness (Rz) and a delustering surface (11b) having a surface opposite to The glossy surface (11a) has a high surface roughness (Rz) exhibiting a so-called mountain contour structure.
光澤面(11a)的表面粗糙度(Rz)是基於沉澱銅的圓柱型鼓(負電極)的表面處理程度而決定，同時去光澤面(11b)的表面粗糙度(Rz)可在電解銅箔(10)的製造中，在電解反應時藉由改變電鍍液的構成材料成份和電流密度而受控制。 The surface roughness (Rz) of the glossy surface (11a) is determined based on the degree of surface treatment of the cylindrical drum (negative electrode) which precipitates copper, and the surface roughness (Rz) of the gloss-removing surface (11b) can be in the electrolytic copper foil. In the production of (10), it is controlled by changing the constituent material composition and current density of the plating solution during the electrolysis reaction.
當電解銅箔(10)的去光澤面(11b)的表面粗糙度(Rz)過高時，介於一主動材料與該電解銅箔(10)間的均勻接觸是不滿意，且可能減少鋰二次電池的放電容量維持率。因此，有需要將表面的粗糙度(Rz)控制在一適當程度，且其最好將電解銅箔(10)的去光澤面(11b)的表面粗糙度(Rz)侷限在約2μm(微米)或較少。 When the surface roughness (Rz) of the de-glazed surface (11b) of the electrolytic copper foil (10) is too high, uniform contact between an active material and the electrolytic copper foil (10) is unsatisfactory, and lithium may be reduced. The discharge capacity retention rate of the secondary battery. Therefore, it is necessary to control the roughness (Rz) of the surface to an appropriate degree, and it is preferable to limit the surface roughness (Rz) of the delustered surface (11b) of the electrolytic copper foil (10) to about 2 μm (micrometer). Or less.
保護層(12)為選擇性形成於銅層(11)的表面，作為電解銅箔(10)的防銹處理，且可利用從鉻酸鹽、苯並三氮唑(BTA)、和矽烷偶聯劑選取之至少一者製成。保護層(12)可對電解銅箔(10)提供防銹特徵和抗熱特徵、及/或具主動材料的黏合強化提升特徵。 The protective layer (12) is selectively formed on the surface of the copper layer (11) as a rustproof treatment of the electrolytic copper foil (10), and can be utilized from chromate, benzotriazole (BTA), and decane At least one of the selected agents is made. The protective layer (12) provides the rust-proof and heat-resistant characteristics of the electrolytic copper foil (10), and/or the adhesion-enhancing enhancement feature of the active material.
電解銅箔的產生 Electrolytic copper foil production
根據本發明之一示範性具體實施例之電解銅箔是藉由介於一圓柱型負電極(採用一預定速率旋轉)與一正電極(配置在相反側)間供應一電鍍液(電解液)而產生，使得銅是被電沉積且還原沉澱在旋轉圓柱型負電極表面，其中硫酸銅的水溶液是當作電鍍液使用，且電解銅箔是約20μm(微米)或較薄(當電解銅箔的厚度減少時，具有黏合其的主動材料的大量集流體可包括在二次電池，其有利於達成高容量，但相對下，一較厚電解銅箔施加於二次電池不適合達成高容量，因此，最好係，電解銅箔的厚度不超過20μm(微米))。施加於實例和比較實例的每個情況如下所述：利用電鍍製成的電解銅箔通常具有兩相反面。即是，電解銅箔具有一光澤側(S面)，其接觸一負電極鼓；及一去光澤側(M面)，其配置在晶粒利用沉澱生長的方向中。電解銅箔的S面和M面的表面粗糙度(Rz)是在小於或等於約2μm(微米)範圍內。 An electrolytic copper foil according to an exemplary embodiment of the present invention is supplied with a plating solution (electrolyte) between a cylindrical negative electrode (rotated at a predetermined rate) and a positive electrode (disposed on the opposite side). Produced so that copper is electrodeposited and reduced precipitated on the surface of a rotating cylindrical negative electrode, wherein an aqueous solution of copper sulfate is used as a plating solution, and the electrolytic copper foil is about 20 μm (micrometer) or thinner (when electrolytic copper foil is used When the thickness is reduced, a large amount of current collector having an active material bonded thereto may be included in the secondary battery, which is advantageous in achieving high capacity, but in contrast, application of a thicker electrolytic copper foil to the secondary battery is not suitable for achieving high capacity, and therefore, Preferably, the thickness of the electrolytic copper foil does not exceed 20 μm (micrometers). Each of the cases applied to the examples and comparative examples is as follows: The electrolytic copper foil produced by electroplating usually has two opposite faces. That is, the electrolytic copper foil has a gloss side (S surface) which contacts a negative electrode drum; and a deluster side (M surface) which is disposed in a direction in which crystal grains are grown by precipitation. The surface roughness (Rz) of the S face and the M face of the electrolytic copper foil is in the range of less than or equal to about 2 μm (micrometer).
(實例) (example)
如表1所示，電解銅箔是在電流密度情況介於約40ASD和70ASD間之下介於約40℃和45℃間溫度範圍利用電鍍液製成，該電鍍液具有介於70g/L(公克/公升)和80g/L(公克/公升)間銅濃度與介於80g/L(公克/公升)和110g/L(公克/公升)間 硫酸濃度、與添加各種不同類型添加劑(無機金屬、均勻劑、與增亮劑)(然而，本發明不必然侷限於此範圍，且在達成本發明目的範圍內可採行適當控制)。 As shown in Table 1, the electrolytic copper foil is formed by using a plating solution having a current density of between about 40 ASD and 70 ASD and a temperature range of about 40 ° C and 45 ° C. The plating solution has a ratio of 70 g/L ( Copper concentration between g/L) and 80g/L (g/L) between 80g/L (g/L) and 110g/L (g/L) The sulfuric acid concentration, and various types of additives (inorganic metal, homogenizer, and brightener) are added (however, the present invention is not necessarily limited to this range, and appropriate control can be employed within the scope of achieving the object of the present invention).
在本說明書中，無機添加劑包括Fe(鐵)、W(鎢)、Zn(鋅)和Mo(鉬)，均勻劑包括凝膠、膠原質和聚乙二醇(PEG，Polyethylene Glycol)，且增亮劑包括雙(3-磺丙基)二硫(SPS)、巰基-丙烷磺酸(MPS)、3-N、N-二甲基硫代氢基甲酰基丙烷磺酸(DPS)。 In the present specification, inorganic additives include Fe (iron), W (tungsten), Zn (zinc), and Mo (molybdenum), and the homogenizer includes gel, collagen, and polyethylene glycol (PEG, Polyethylene Glycol), and Brighteners include bis(3-sulfopropyl)disulfide (SPS), mercapto-propanesulfonic acid (MPS), 3-N, N-dimethylthiohydroformylpropane sulfonic acid (DPS).
為了保護(例如，防銹)目的，利用前述製程情況製成的電解銅箔會在表面進行鉻化處理。 For the purpose of protection (for example, rust prevention), the electrolytic copper foil produced by the above process conditions is chromed on the surface.
(比較實例) (Comparative example)
如表1所示，在約45℃溫度，介於約50ASD和70ASD間的電流密度情況之下，電解銅箔可使用添加含有各種不同類型添加劑(相同於實例的添加劑)的介於70g/L(公克/公升)和80g/L(公克/公升)間銅濃度、與介於95g/L(公克/公升)和105g/L(公克/公升)間硫酸濃度的電鍍液製成。 As shown in Table 1, at a temperature of about 45 ° C, at a current density between about 50 ASD and 70 ASD, the electrolytic copper foil can be used at 70 g/L with additives containing various types of additives (same as the examples). It is made of a copper concentration between (g/L) and 80 g/L (g/L), and a plating solution having a sulfuric acid concentration of between 95 g/L (g/L) and 105 g/L (g/L).
斷裂模數特徵的測量 Measurement of fracture modulus characteristics
如在前述製程情況之下產生之根據本發明之實例的電解銅箔、與根據比較實例之電解銅箔會經由測量以決定斷裂模數特徵(f)。 The electrolytic copper foil according to the example of the present invention produced under the foregoing process conditions, and the electrolytic copper foil according to the comparative example, are measured to determine the modulus of rupture (f).
電解銅箔的斷裂模數特徵(f)係使用根據一標準測量方法的萬能材料試驗機(UTM，Universal Testing Machine)進行測量，且在 此例證中，如同應用UTM情況，計算長度是50mm(公釐)，寬度是12.7mm(公釐)，且測試速度是2mm/min(公釐/分)。 The modulus of rupture (f) of the electrolytic copper foil is measured using a universal material testing machine (UTM, Universal Testing Machine) according to a standard measurement method, and In this example, as in the case of UTM application, the calculated length is 50 mm (millimeter), the width is 12.7 mm (millimeter), and the test speed is 2 mm/min (mm/min).
首先於190℃執行退火達1小時，然後測量電解銅箔的斷裂模數特徵(f)，使得在前述情況之下，根據實例/比較實例所產生電解銅箔的情況等同於完成鋰二次電池內的情況。即是，鋰二次電池可通過高溫狀態於鋰二次電池的製程當中維持一預定時段的製程，且為了建立一類似情況，針對電解銅箔執行退火。 First, annealing was performed at 190 ° C for 1 hour, and then the modulus of rupture (f) of the electrolytic copper foil was measured, so that in the foregoing case, the case of the electrolytic copper foil produced according to the example/comparative example was equivalent to the completion of the lithium secondary battery. The situation inside. That is, the lithium secondary battery can be maintained in a high temperature state in the process of the lithium secondary battery for a predetermined period of time, and in order to establish a similar situation, annealing is performed for the electrolytic copper foil.
測量進行退火製程的電解銅箔斷裂模數特徵(f)的結果顯示在下表2。 The results of measuring the modulus of rupture (f) of the electrolytic copper foil subjected to the annealing process are shown in Table 2 below.
請即參考表2的結果，實例1至6的電解銅箔呈現斷裂模數特徵介於5.0和18.0間範圍，然而，比較實例1至3的電解銅箔呈現斷裂模數特徵小於5.0，且比較實例4的電解銅箔呈現斷裂模數 特徵超過18.0。 Referring to the results of Table 2, the electrolytic copper foils of Examples 1 to 6 exhibited a modulus of rupture characteristic ranging between 5.0 and 18.0. However, the electrolytic copper foils of Comparative Examples 1 to 3 exhibited a modulus of fracture characteristic of less than 5.0, and were compared. The electrolytic copper foil of Example 4 exhibits a modulus of rupture Features over 18.0.
鋰二次電池的製造 Manufacturing of lithium secondary batteries
一正電極板和一負電極板的製造 Manufacture of a positive electrode plate and a negative electrode plate
(一正電極材料混合的成份) (a component of a positive electrode material mixed)
(一負電極材料混合的成份) (a component mixed with a negative electrode material)
N-甲基吡咯烷酮添加於前述成份以備製一漿料，然後在溶劑蒸發、滾製，且切割成一預定尺寸以後，再塗裝於一正電極集流體(利用鋁箔製成)與一負電極集流體(利用電解銅箔製成)的每個表面，以製造一正電極板與一負電極頭。 N-methylpyrrolidone is added to the above ingredients to prepare a slurry, which is then applied to a positive electrode current collector (made of aluminum foil) and a negative electrode after the solvent is evaporated, rolled, and cut into a predetermined size. Each surface of the current collector (made of electrolytic copper foil) is used to manufacture a positive electrode plate and a negative electrode tip.
鋰二次電的組件 Lithium secondary component
正電極板、一分隔板(一親水性多孔聚乙烯薄膜)、與負電極板係循序疊置且纏繞在一起，且在電解液灌注/密封以後，然後置入一容器，以完成一圓柱型電池。該電池是一般圓圓柱型18650格式。 a positive electrode plate, a separator plate (a hydrophilic porous polyethylene film), and a negative electrode plate are sequentially stacked and entangled, and after the electrolyte is poured/sealed, then placed in a container to complete a cylinder Type battery. The battery is a generally round cylindrical 18650 format.
在本說明書中，電解液為1M LiPF6採用1：1體積比而溶解在碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的混合溶劑的溶液。 In the present specification, the electrolytic solution is a solution in which 1 M LiPF 6 is dissolved in a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) in a 1:1 volume ratio.
充電/放電測試 Charging/discharging test
在前述情況之下製造的鋰二次電池之中，基於根據如表1顯示實例1至6的電解銅箔，使用負電極集流體製造的鋰二次電池(根據本發明之實例的二次電池)分別稱為根據實例1至6的鋰二次電池。 Among the lithium secondary batteries fabricated under the foregoing circumstances, lithium secondary batteries fabricated using a negative electrode current collector based on the electrolytic copper foils of Examples 1 to 6 as shown in Table 1 (secondary batteries according to examples of the present invention) ) Lithium secondary batteries according to Examples 1 to 6 are respectively referred to.
同樣地，基於根據如表1顯示比較實例1至4的電解銅箔，使用負電極集流體製造的鋰二次電池分別稱為根據比較實例1至4的鋰二次電池。 Also, based on the electrolytic copper foils according to Comparative Examples 1 to 4 as shown in Table 1, lithium secondary batteries fabricated using the negative electrode current collectors were respectively referred to as lithium secondary batteries according to Comparative Examples 1 to 4.
針對如前述製造的鋰二次電池進行500個重複週期的充電/放電測試。在此例證中，充電是在充電電壓4.3V(伏特)和充電電流0.2C(其中電池是在5小時後完全充電)的情況之下，採用定電流和定電壓(CCCV，Constant Current & Constant Voltage)模式進行，且放電是在放電電壓3.0V(伏特)和放電電流0.5C的情況之下，採用定電流(CC，Constant Current)模式進行(其中電池是在2小時內完全放電)。 A charge/discharge test of 500 cycles was performed for the lithium secondary battery fabricated as described above. In this example, charging is performed at a charging voltage of 4.3 V (volts) and a charging current of 0.2 C (where the battery is fully charged after 5 hours), using constant current and constant voltage (CCCV, Constant Current & Constant Voltage). The mode is performed, and the discharge is performed in a constant current (CC) mode with a discharge voltage of 3.0 V (volts) and a discharge current of 0.5 C (where the battery is completely discharged within 2 hours).
在完成重複充電和放電之後，鋰二次電池經測量以決定容量維持率，其為熱產生的程度，且不管裂開是否發生在構成集流體的電解銅箔，且其結果顯示在下表3。 After the repeated charging and discharging were completed, the lithium secondary battery was measured to determine the capacity retention ratio, which is the degree of heat generation, and whether or not cracking occurred in the electrolytic copper foil constituting the current collector, and the results thereof are shown in Table 3 below.
(1~6：本發明的實例；1*~4*：比較實例) (1~6: an example of the present invention; 1*~4*: comparative example)
請即參考上表3，在電解銅箔的斷裂模數特徵(f)是介於5.0和18.0間範圍的情況，根據本發明之實例的鋰二次電池(實例1至6)在500個週期充電和放電以後在集流體沒有裂開情況，且維持基於最初容量的從約84%至93%的高容量維持率(當執行500個週期充電和放電時，二次電池通常呈現介於約80%和90%間的容量維持率，且如果缺陷發生在二次電池，容量維持率明顯降低，呈現明顯不同於正常值)。 Referring to Table 3 above, in the case where the modulus of rupture (f) of the electrolytic copper foil is in the range of 5.0 and 18.0, the lithium secondary battery (Examples 1 to 6) according to the example of the present invention is in 500 cycles. After the charging and discharging, there is no cracking in the current collector, and the high capacity maintenance ratio from about 84% to 93% based on the initial capacity is maintained (the secondary battery usually exhibits about 80 when performing 500 cycles of charging and discharging). The capacity retention ratio between % and 90%, and if the defect occurs in the secondary battery, the capacity retention rate is significantly lowered, which is significantly different from the normal value).
同時，採用恆溫室內進行充電/放電測試的方式來測量熱產生，且實例1至6的鋰二次電池呈現介於25℃和28℃間範圍的表 面溫度，其符合正常溫度範圍(小於或等於約30℃的溫度認為是在正常範圍內，且即使發生暫時性溫度增加，除非有特別不正常發生，否則表面溫度不會超過40℃)。 At the same time, the heat generation was measured by a charging/discharging test in a constant temperature chamber, and the lithium secondary batteries of Examples 1 to 6 exhibited a range between 25 ° C and 28 ° C. The surface temperature, which conforms to the normal temperature range (temperature less than or equal to about 30 ° C is considered to be within the normal range, and even if a temporary temperature increase occurs, the surface temperature does not exceed 40 ° C unless there is a particular abnormality.)
對照下，由於重複充電和放電，在電解銅箔的斷裂模數特徵(f)小於5.0的情況，根據比較實例的鋰二次電池(比較實例1至3)在集流體會經歷裂開，且基於最初的容量，呈現從約24%至42%位準的容量維持率，造成二次電池功能明顯損失。在集流體產生的裂開會造成黏結集流體的電極主動材料剝落，且裂開產生會直接影響容量維持率的降低。 In contrast, in the case where the piezoelectric modulus of the electrolytic copper foil (f) is less than 5.0 due to repeated charging and discharging, the lithium secondary battery according to the comparative example (Comparative Examples 1 to 3) undergoes cracking at the current collector, and Based on the initial capacity, a capacity retention ratio from about 24% to 42% is presented, resulting in a significant loss of secondary battery function. The splitting of the current generated by the current collector causes the electrode active material to peel off, and the cracking occurs directly affects the decrease in the capacity retention rate.
儘管重複充電和放電，在電解銅箔的斷裂模數特徵(f)超過18.0的情況，根據比較實例的鋰二次電池(比較實例4)可避免裂開且維持相當高容量維持率，但在熱產生的測量中，呈現約41℃的溫度，其通常認為偏離正常範圍30℃。不正常熱產生現象可能使鋰二次電池性能惡化且增加意外事件的風險。 In spite of repeated charging and discharging, in the case where the modulus of rupture (f) of the electrolytic copper foil exceeds 18.0, the lithium secondary battery according to the comparative example (Comparative Example 4) can avoid cracking and maintain a relatively high capacity retention rate, but In the measurement of heat generation, a temperature of about 41 ° C is exhibited, which is generally considered to deviate from the normal range by 30 ° C. An abnormal heat generation phenomenon may deteriorate the performance of the lithium secondary battery and increase the risk of an accident.
從實驗結果，可清楚明白，當電解銅箔(10)的斷裂模數特徵(f)維持在預定範圍(介於5.0和18.0間)內，可甚至在重複充電和放電造成嚴苛的情況之下維持二次電池的效能，因此，可確保二次電池使用時的安全性。 From the experimental results, it is clear that when the modulus of rupture (f) of the electrolytic copper foil (10) is maintained within a predetermined range (between 5.0 and 18.0), even in the case of severe charging due to repeated charging and discharging The performance of the secondary battery is maintained, and therefore, the safety of the secondary battery can be ensured.
雖然本發明只利用前面參考的有限具體實施例和圖式描述，不過本發明並未侷限於此，且應瞭解，熟諳此技者可進行各種不同變更與修改，不致悖離本發明、文後申請專利範圍及其相關的精神與範疇。 The present invention is not limited to the specific embodiments and drawings described above, but the present invention is not limited thereto, and it should be understood that various changes and modifications may be made without departing from the invention. The scope of the patent application and its related spirit and scope.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ??10-2014-0086970 | 2014-07-10 | ||
| KR1020140086970A KR101737028B1 (en) | 2014-07-10 | 2014-07-10 | Method for producing electrolytic copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201602418A TW201602418A (en) | 2016-01-16 |
| TWI639731B true TWI639731B (en) | 2018-11-01 |
Family
ID=55064395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104118592A TWI639731B (en) | 2014-07-10 | 2015-06-09 | Electrolytic copper foil and method for producing the same, and current collector for lithium secondary battery and secondary battery comprising the electrolytic copper foil |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2017526115A (en) |
| KR (1) | KR101737028B1 (en) |
| CN (1) | CN106536791A (en) |
| TW (1) | TWI639731B (en) |
| WO (1) | WO2016006793A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101734840B1 (en) * | 2016-11-11 | 2017-05-15 | 일진머티리얼즈 주식회사 | Electrolytic copper foil of secondary battery enhanced for flexibility resistance and manufacturing method thereof |
| KR101733410B1 (en) * | 2016-11-11 | 2017-05-10 | 일진머티리얼즈 주식회사 | Electrolytic copper foil of secondary battery enhanced for low temperature property and manufacturing method thereof |
| KR101733408B1 (en) * | 2016-11-11 | 2017-05-10 | 일진머티리얼즈 주식회사 | Electrolytic Copper Foil for secondary battery and manufacturing method thereof |
| KR101733409B1 (en) * | 2016-11-11 | 2017-05-10 | 일진머티리얼즈 주식회사 | Electrolytic Copper Foil of secondary battery and manufacturing method thereof |
| CN106960960A (en) * | 2017-05-11 | 2017-07-18 | 天津理工大学 | A kind of preparation method of the flexible current-collecting body for the cycle performance for improving lithium ion battery negative material |
| KR102473030B1 (en) * | 2017-08-30 | 2022-11-30 | 에스케이넥실리스 주식회사 | Copper Film, Manufacturing Methods Thereof, And Anode For Li Secondary Battery Comprising The Same |
| KR102483089B1 (en) * | 2018-01-31 | 2022-12-29 | 에스케이넥실리스 주식회사 | Copper Film With Enhanced Handling Properties At Subsequent Process, And Manufacturing Methods Thereof |
| TWI705160B (en) * | 2019-12-09 | 2020-09-21 | 長春石油化學股份有限公司 | Electrolytic copper foil and electrode and copper-clad laminate comprising the same |
| KR102559954B1 (en) | 2021-11-24 | 2023-07-25 | 동아대학교 산학협력단 | Method of manufacturing high elongation metal foil and high elongation metal foil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101669237A (en) * | 2007-04-20 | 2010-03-10 | 日矿金属株式会社 | Electrolytic copper foil for lithium rechargeable battery and process for producing the copper foil |
| CN102959135A (en) * | 2010-07-01 | 2013-03-06 | 三井金属矿业株式会社 | Electrodeposited copper foil and process for production thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3850321B2 (en) * | 2002-03-19 | 2006-11-29 | 日本電解株式会社 | Secondary battery |
| WO2006106956A1 (en) * | 2005-03-31 | 2006-10-12 | Mitsui Mining & Smelting Co., Ltd | Electrolytic copper foil and process for producing electrolytic copper foil, surface treated elctrolytic copper foil using said electrolytic copper foil, and copper-clad laminate plate and printed wiring board using said surface treated electrolytic copper foil |
| JP2007146289A (en) * | 2005-10-31 | 2007-06-14 | Mitsui Mining & Smelting Co Ltd | Method for manufacture of electrolytic copper foil, electrolytic copper foil manufactured by the method, surface-treated copper foil manufactured using the electrolytic copper foil, and copper-clad laminate manufactured using the electrolytic copper foil or surface-treated copper foil |
| JP5352542B2 (en) * | 2010-07-15 | 2013-11-27 | エル エス エムトロン リミテッド | Copper foil for current collector of lithium secondary battery |
| JP5508358B2 (en) * | 2011-07-29 | 2014-05-28 | 株式会社Ｓｈカッパープロダクツ | Rolled copper foil, method for producing the same, and lithium ion secondary battery negative electrode using the rolled copper foil |
| KR20140078883A (en) * | 2012-12-18 | 2014-06-26 | 주식회사 엘지화학 | Method of Manufacturing Electrolytic Copper Foil for Current Collector of Secondary Battery |
-
2014
- 2014-07-10 KR KR1020140086970A patent/KR101737028B1/en active IP Right Grant
-
2015
- 2015-03-26 WO PCT/KR2015/002986 patent/WO2016006793A1/en active Application Filing
- 2015-03-26 CN CN201580037574.9A patent/CN106536791A/en active Pending
- 2015-03-26 JP JP2017501022A patent/JP2017526115A/en active Pending
- 2015-06-09 TW TW104118592A patent/TWI639731B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101669237A (en) * | 2007-04-20 | 2010-03-10 | 日矿金属株式会社 | Electrolytic copper foil for lithium rechargeable battery and process for producing the copper foil |
| CN102959135A (en) * | 2010-07-01 | 2013-03-06 | 三井金属矿业株式会社 | Electrodeposited copper foil and process for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160007047A (en) | 2016-01-20 |
| CN106536791A (en) | 2017-03-22 |
| JP2017526115A (en) | 2017-09-07 |
| TW201602418A (en) | 2016-01-16 |
| KR101737028B1 (en) | 2017-05-17 |
| WO2016006793A1 (en) | 2016-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI639731B (en) | Electrolytic copper foil and method for producing the same, and current collector for lithium secondary battery and secondary battery comprising the electrolytic copper foil | |
| JP6587701B2 (en) | Electrolytic copper foil for lithium secondary battery and lithium secondary battery including the same | |
| JP5351012B2 (en) | Electrolytic copper foil for lithium secondary battery and method for producing the copper foil | |
| KR101890775B1 (en) | Electrolytic copper foil and method for producing the same | |
| KR101660335B1 (en) | Electrolytic copper foil | |
| TW201918588A (en) | Electrodeposited copper foil and method for producing the same and secondary battery comprising the electrodeposited copper foil | |
| JPWO2015060300A1 (en) | Aluminum alloy foil for electrode current collector and method for producing the same | |
| US11108052B2 (en) | Rolled copper foil for negative electrode current collector of secondary battery, negative electrode of secondary battery and secondary battery using the rolled copper, and method for manufacturing rolled copper foil for negative electrode current collector of secondary battery | |
| KR102109379B1 (en) | Electrolytic copper foil and Current collector for lithium secondary battery and Secondary battery comprising the electrolytic copper foil | |
| JPWO2013018164A1 (en) | Aluminum alloy foil for electrode current collector and method for producing the same | |
| JPWO2013018165A1 (en) | Aluminum alloy foil for electrode current collector and method for producing the same | |
| TW201448338A (en) | Copper foil, anode for lithium ion battery, and lithium ion secondary battery | |
| JP2010103061A (en) | Negative electrode copper alloy foil of secondary battery and manufacturing method for the same | |
| JP4413552B2 (en) | Electrolytic copper foil and electrolytic copper foil for secondary battery current collector | |
| JP6067910B1 (en) | Electrolytic copper foil and lithium ion secondary battery using the electrolytic copper foil | |
| KR102643400B1 (en) | Rolled copper foil for lithium ion battery current collector and lithium ion battery | |
| JP5830100B2 (en) | Aluminum alloy foil for electrode current collector and method for producing the same | |
| JP2019536211A (en) | Electrolytic copper foil for secondary battery and method for producing the same | |
| KR20240025712A (en) | Rolled copper foil for secondary battery negative electrode current collectors, secondary battery negative electrode current collector and secondary battery each using same, and method for manufacturing rolled copper foil for secondary battery negative electrode current collectors | |
| KR102299094B1 (en) | Rolled copper foil for lithium ion battery current collector and lithium ion battery | |
| JP2019199648A (en) | Electrolytic copper foil, and secondary battery using the same | |
| JP2020502728A (en) | Electrodeposited copper foil for secondary battery with excellent bending resistance and method for producing the same | |
| TWI686003B (en) | Rolled copper foil for lithium ion battery collector and lithium ion battery |