WO2016204405A1 - Feuille de cuivre électrolytique pour une batterie secondaire au lithium et batterie secondaire au lithium contenant ladite feuille - Google Patents

Feuille de cuivre électrolytique pour une batterie secondaire au lithium et batterie secondaire au lithium contenant ladite feuille Download PDF

Info

Publication number
WO2016204405A1
WO2016204405A1 PCT/KR2016/004925 KR2016004925W WO2016204405A1 WO 2016204405 A1 WO2016204405 A1 WO 2016204405A1 KR 2016004925 W KR2016004925 W KR 2016004925W WO 2016204405 A1 WO2016204405 A1 WO 2016204405A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium secondary
copper foil
electrolytic copper
secondary battery
secondary batteries
Prior art date
Application number
PCT/KR2016/004925
Other languages
English (en)
Korean (ko)
Inventor
김승민
김수열
김대영
이정길
Original Assignee
엘에스엠트론 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020160049472A external-priority patent/KR102122425B1/ko
Application filed by 엘에스엠트론 주식회사 filed Critical 엘에스엠트론 주식회사
Priority to CN201680000866.XA priority Critical patent/CN106663816B/zh
Priority to US15/315,774 priority patent/US10418635B2/en
Priority to PL16811818T priority patent/PL3312920T3/pl
Priority to JP2017565096A priority patent/JP6584531B2/ja
Priority to EP16811818.0A priority patent/EP3312920B1/fr
Publication of WO2016204405A1 publication Critical patent/WO2016204405A1/fr

Links

Images

Classifications

    • 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
    • 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

Definitions

  • the present invention relates to an electrolytic copper foil for a lithium secondary battery and a lithium secondary battery comprising the same, and more particularly, an electrolytic copper foil for a lithium secondary battery having an elongation of a predetermined level or more after receiving a thermal history experienced in the actual manufacturing process of a lithium secondary battery. It relates to a lithium secondary battery comprising the same.
  • This application claims priority based on Korean Patent Application No. 10-2015-0086856 filed on June 18, 2015 and Korean Patent Application No. 10-2016-0049472 filed on April 22, 2016. All content disclosed in the specification and drawings of an application is incorporated in this application.
  • graphite-based materials are mainly used as negative electrode materials of lithium secondary batteries.
  • graphite-based negative electrode materials have a small battery capacity per weight, and thus cannot meet the demand for large capacity of mobile batteries.
  • the application of the silicon-based negative electrode active material is actively studied as a next-generation negative electrode material because the capacity per weight of the silicon-based negative electrode active material is much larger than that of graphite.
  • the Si-based negative electrode material when used as the negative electrode active material, the volume expansion of the negative electrode is severe, and when it is commercialized with copper foil, the charge and discharge efficiency is significantly reduced due to the tearing of the negative electrode current collector during charge and discharge.
  • a polyimide resin that can catch the volume expansion of the negative electrode material is used as a binder.
  • an electrolytic copper foil for a lithium secondary battery applied as a negative electrode current collector of a lithium secondary battery may have a heat history for a predetermined time at a high temperature of about 300 ° C.
  • an electrolytic copper foil for a lithium secondary battery it should have suitable physical properties.
  • an object of the present invention is to obtain an electrolytic copper foil for a lithium secondary battery capable of maintaining excellent physical properties of a predetermined level or more even after receiving a thermal history at a high temperature.
  • the present inventors have conducted research to achieve the above technical problem, and as a result, when the electrolytic copper foil for a lithium secondary battery subjected to heat history at a high temperature has an elongation of a certain level or more, even if the volume expansion of the negative electrode material occurs during charging and discharging of the secondary battery It was found that the tearing of the negative electrode current collector can be prevented from occurring.
  • the electrolytic copper foil for lithium secondary batteries is an electrolytic copper foil for lithium secondary batteries that is applied as a negative electrode current collector of a lithium secondary battery, and the elongation after heat treatment at about 300 ° C. for 30 minutes corresponds to 5% or more. do.
  • the lithium secondary battery electrolytic copper foil may have an elongation after heat treatment at 300 ° C. for 30 minutes in a range of 5% to 30%.
  • the lithium secondary battery electrolytic copper foil may have a breaking strength after heat treatment at 300 ° C. for 30 minutes in a range of 19 kgf / mm 2 to 26 kgf / mm 2 .
  • the lithium secondary battery electrolytic copper foil may have a breaking strength ratio ((breaking strength / yield strength) ⁇ 100) after heat treatment at 300 ° C. for 30 minutes in a range of 110% to 165%.
  • the said electrolytic copper foil for lithium secondary batteries can be equipped with the antirust layer containing any 1 or more types of chromium (Cr), a silane compound, and a nitrogen compound on both surfaces.
  • the thickness of the electrolytic copper foil for lithium secondary batteries may range from 3 ⁇ m to 30 ⁇ m.
  • Surface roughness of both surfaces of the electrolytic copper foil for the lithium secondary battery may be 3.5 ⁇ m or less based on Rz.
  • the above-mentioned electrolytic copper foil for a lithium secondary battery is applied as a negative electrode current collector.
  • an electrolytic copper foil for a lithium secondary battery and a lithium secondary battery manufactured using the same which can maintain excellent quality even after receiving a high temperature thermal history that is necessarily passed in the manufacturing process of the lithium secondary battery.
  • FIG. 1 is a cross-sectional view showing an electrolytic copper foil for a lithium secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing a state in which a rust-preventing layer is formed on the surface of an electrolytic copper foil for a lithium secondary battery according to an embodiment of the present invention.
  • Figure 3 is a graph showing the physical properties after the lithium secondary battery electrolytic copper foil according to an embodiment of the present invention after receiving a high temperature thermal history.
  • FIG. 1 is a cross-sectional view showing an electrolytic copper foil for a lithium secondary battery according to an embodiment of the present invention.
  • Electrolytic copper foil 1 for a lithium secondary battery according to an embodiment of the present invention shown in FIG. 1 is preferably used as a negative electrode current collector of a lithium secondary battery. That is, in a lithium secondary battery, it is preferable that an electrolytic copper foil is used as a negative electrode collector couple
  • a foil made of aluminum (Al) is generally used as a positive electrode current collector combined with the positive electrode active material.
  • the case where the said electrolytic copper foil 1 for lithium secondary batteries corresponds to the negative electrode electrical power collector applied to a lithium secondary battery is demonstrated as an example.
  • the elongation measured after heat treatment for about 30 minutes at a high temperature of about 300 ° C. appears to be about 5% or more.
  • 300 ° C. is obtained by coating a negative electrode active material on an electrolytic copper foil during the manufacturing process of a real lithium secondary battery (a Si-based negative electrode material and a lithium secondary battery in which a polyimide-based resin is used as a binder to catch volume expansion of the Si-based negative electrode material). It corresponds to the temperature applied at the time of post-drying, and after the heat treatment, an elongation of approximately 5% or more may be used to prevent the tearing of the electrolytic copper foil during the secondary battery charge / discharge test.
  • the lithium secondary battery electrolytic copper foil 1 is preferably manufactured such that the elongation measured after the heat treatment for about 30 minutes at a high temperature of about 300 ° C. appears to be about 30% or less. Do.
  • the electrode is removed from the battery manufacturing line. Wrinkles occur in the electrode during the transfer process.
  • the breaking strength of the lithium secondary battery electrolytic copper foil 1 is preferably limited to approximately 19kgf / mm 2 to 26kgf / mm 2 range.
  • the electrolytic copper foil may not withstand the tensile stress applied during winding of the electrolytic copper foil and / or the electrode, thereby causing tearing of the electrolytic copper foil. have.
  • the value obtained by multiplying the breaking strength ratio that is, the breaking strength divided by the yield strength, by the lithium secondary battery electrolytic copper foil 1 by the yield strength by 100 is approximately 110% to 165%.
  • the electrolytic copper foil In producing the electrolytic copper foil, it is almost technically impossible to make the fracture strength ratio after heat treatment at approximately 300 ° C less than about 110%, and when the fracture strength ratio after heat treatment exceeds 165%, the Si-based negative electrode After recoating and drying, the electrolytic copper foil may be easily deformed and wrinkles may be generated in the process of transferring the electrode on the battery manufacturing line.
  • the electrolytic copper foil for a lithium secondary battery has a suitable physical property in a manufacturing process so that there is no problem in reliability during manufacturing of the lithium secondary battery even after receiving a thermal history at a high temperature of approximately 300 ° C. Corresponds to a well-controlled electrolytic copper foil.
  • the surface roughness of both surfaces of the lithium secondary battery electrolytic copper foil according to an embodiment of the present invention is preferably about 0.2 ⁇ m to 3.5 ⁇ m based on Rz (ten point average roughness).
  • the surface roughness exceeds approximately 3.5 ⁇ m, uniform coating of the active material may not be performed on the surface 1a of the electrolytic copper foil due to the high roughness, and thus the adhesion may be lowered. If not, the discharge capacity retention rate of the manufactured lithium secondary battery may decrease.
  • the thickness of the said electrolytic copper foil for lithium secondary batteries is about 3 micrometers-30 micrometers.
  • the thickness of the electrodeposited copper foil is too thin, less than about 3 ⁇ m, handling of the electrodeposited copper foil becomes difficult in the battery manufacturing process, and thus workability may be degraded. On the contrary, when the thickness of the electrodeposited copper foil exceeds about 30 ⁇ m, the electrodeposited copper foil may be collected. When used as a whole, there is a problem in that it becomes difficult to manufacture a high capacity battery due to the increase in volume due to the thickness of the current collector.
  • an electrolytic copper foil 1 for a lithium secondary battery may include an antirust layer 2 formed on the surface 1a thereof.
  • the rustproof layer (2) is selectively formed on the surface (1a) of the electrolytic copper foil for the rust prevention treatment of the electrolytic copper foil (1) for lithium secondary battery, and contains any one or more of chromium (Cr), a silane compound and a nitrogen compound. can do.
  • the rustproof layer 2 may play a role of imparting not only rustproof properties to the electrolytic copper foil 1 for lithium secondary batteries, but also heat resistance and / or an increase in bonding strength with the active material.
  • An electrolytic copper foil for a lithium secondary battery according to an embodiment and a comparative example is manufactured by using a milling machine having a structure including a positive electrode plate positioned at a predetermined interval with respect to a rotating drum and a drum in an electrolytic cell.
  • the electrolyte for producing an electrolytic copper foil for a lithium secondary battery according to the embodiment has a concentration of 1 g of TOC in copper sulphate containing 50 to 100 g / L of copper and 50 to 150 g / L of sulfuric acid. By limiting it to / L or less, the concentration of organic impurities is limited to 1 g / L or less.
  • the concentration of organic impurities is limited to 1 g / L or less.
  • the current density applied at the time of electrodeposition of the electrolytic copper foil which concerns on an Example shall be 30ASD-80ASD, and the temperature of electrolyte solution is adjusted to 40-70 degreeC.
  • the organic additives include HEC (Hydroxyethyl Cellulose), 3- (Benzothiazolyl-2-mercapto) -propyl-sulfonic acid, and polymer nitrides (eg, gelatin).
  • the additive is HEC 2 ⁇ 15mg / L, (3- (Benzothiazolyl-2-mercapto) -propyl-sulfonic acid 2 ⁇ 15mg / L, high molecular weight gelatin (Gelatin) (2300g / mole) 5 ⁇ 20mg / L is preferably used.
  • an electrolytic copper foil for a lithium secondary battery corresponding to the comparative example a method different from the above-described manufacturing method is applied, and specifically, copper sulfate (50 ⁇ 100g / L copper, 50 used as the electrolyte in the process of pulverization
  • concentration of TOC, an organic impurity in ⁇ 150 g / L sulfuric acid) exceeds 1 g / L or the current density applied during electrodeposition of the electrolytic copper foil is outside the range of 30 ASD to 80 ASD.
  • composition and electrolytic conditions of the specific electrolyte solution for milling the electrolytic copper foil which concerns on such an Example and a comparative example are as follows.
  • the electrolytic copper foil 1 according to the embodiment and the comparative example can form the rust-proof layer 2 on the surface (1a) as shown in FIG.
  • the negative electrode material was coated on an electrolytic copper foil and dried at 300 ° C. to make jelly rolls using a roll-to-roll battery manufacturing facility, and the winding tension was set to 160 N at a speed of 5 to 10 mpm. It was. When winding the electrolytic copper foil coated with the negative electrode material 1,000m it was judged that the occurrence of wrinkles and the case of tearing was bad.
  • the lithium secondary battery samples were prepared by the corresponding process, after 200 charge / discharge tests at 0.2C, the lithium secondary battery was decomposed to determine whether the copper foil coated with the negative electrode material was torn, and was determined to be defective.
  • Example 6 when comparing Example 6 and Comparative Examples 6 to 8 of Table 2, the failure strength of the electrolytic copper foil after the heat treatment should not exceed 165%. It can be seen (However, the breaking strength rate can not technically fall below 110% in the electrolytic copper foil subjected to heat treatment at 300 ° C. for 30 minutes).
  • the electrolytic copper foil for lithium secondary batteries has an elongation in the range of approximately 5% to 30% after heat treatment at approximately 300 ° C., and approximately 19 kgf / mm 2 to 26 kgf / mm 2. It can be seen that having a break strength of, and when manufactured to have a break strength ratio in the range of about 110% to 165%, it can have an excellent quality suitable for the production of a lithium secondary battery.
  • the present invention relates to an electrolytic copper foil for a lithium secondary battery, which is a negative electrode current collector material applied to a lithium secondary battery, and a lithium secondary battery including the same.

Landscapes

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

Abstract

Selon un mode de réalisation de la présente invention, une feuille de cuivre électrolytique pour batterie secondaire au lithium est appliquée sous la forme d'un collecteur de courant d'anode d'une batterie secondaire au lithium, et présente un taux d'allongement compris entre 5 % et 30 % après un traitement thermique à environ 300 °C pendant 30 minutes.
PCT/KR2016/004925 2015-06-18 2016-05-11 Feuille de cuivre électrolytique pour une batterie secondaire au lithium et batterie secondaire au lithium contenant ladite feuille WO2016204405A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201680000866.XA CN106663816B (zh) 2015-06-18 2016-05-11 用于锂二次电池的电解铜箔及包含该电解铜箔的锂二次电池
US15/315,774 US10418635B2 (en) 2015-06-18 2016-05-11 Electrolytic copper foil for lithium secondary battery and lithium secondary battery comprising the same
PL16811818T PL3312920T3 (pl) 2015-06-18 2016-05-11 Elektrolityczna folia miedziana do akumulatora litowego oraz zawierający ją akumulator litowy
JP2017565096A JP6584531B2 (ja) 2015-06-18 2016-05-11 リチウム二次電池用の電解銅箔及びこれを含むリチウム二次電池
EP16811818.0A EP3312920B1 (fr) 2015-06-18 2016-05-11 Feuille de cuivre électrolytique pour une batterie secondaire au lithium et batterie secondaire au lithium contenant ladite feuille

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2015-0086856 2015-06-18
KR20150086856 2015-06-18
KR1020160049472A KR102122425B1 (ko) 2015-06-18 2016-04-22 리튬 이차전지용 전해동박 및 이를 포함하는 리튬 이차전지
KR10-2016-0049472 2016-04-22

Publications (1)

Publication Number Publication Date
WO2016204405A1 true WO2016204405A1 (fr) 2016-12-22

Family

ID=57545939

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/004925 WO2016204405A1 (fr) 2015-06-18 2016-05-11 Feuille de cuivre électrolytique pour une batterie secondaire au lithium et batterie secondaire au lithium contenant ladite feuille

Country Status (1)

Country Link
WO (1) WO2016204405A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000182623A (ja) * 1998-12-11 2000-06-30 Nippon Denkai Kk 電解銅箔、二次電池の集電体用銅箔及び二次電池
KR20090125823A (ko) * 2007-04-20 2009-12-07 닛코 킨조쿠 가부시키가이샤 리튬 2차 전지용 전해 구리박 및 그 구리박의 제조 방법
KR20140007507A (ko) * 2010-07-01 2014-01-17 미쓰이금속광업주식회사 전해 동박 및 그 제조 방법
KR20140084216A (ko) * 2011-10-31 2014-07-04 후루카와 덴키 고교 가부시키가이샤 고강도, 고내열 전해 동박 및 그 제조방법
KR20150062227A (ko) * 2013-11-28 2015-06-08 일진머티리얼즈 주식회사 전해동박, 이를 포함하는 전기부품 및 전지, 및 전해동박 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000182623A (ja) * 1998-12-11 2000-06-30 Nippon Denkai Kk 電解銅箔、二次電池の集電体用銅箔及び二次電池
KR20090125823A (ko) * 2007-04-20 2009-12-07 닛코 킨조쿠 가부시키가이샤 리튬 2차 전지용 전해 구리박 및 그 구리박의 제조 방법
KR20140007507A (ko) * 2010-07-01 2014-01-17 미쓰이금속광업주식회사 전해 동박 및 그 제조 방법
KR20140084216A (ko) * 2011-10-31 2014-07-04 후루카와 덴키 고교 가부시키가이샤 고강도, 고내열 전해 동박 및 그 제조방법
KR20150062227A (ko) * 2013-11-28 2015-06-08 일진머티리얼즈 주식회사 전해동박, 이를 포함하는 전기부품 및 전지, 및 전해동박 제조방법

Similar Documents

Publication Publication Date Title
JP6584531B2 (ja) リチウム二次電池用の電解銅箔及びこれを含むリチウム二次電池
WO2016208858A1 (fr) Feuille de cuivre électrolytique pour batterie secondaire au lithium et batterie secondaire au lithium comprenant celle-ci
WO2013154253A1 (fr) Electrode comprenant une couche de revêtement poreux, procédé de fabrication de celle-ci, et dispositif électrochimique la comprenant
WO2011065765A2 (fr) Procédé pour fabriquer un séparateur, séparateur fabriqué selon celui-ci, et dispositif électrochimique comprenant le séparateur
EP3605655B1 (fr) Film composite poreux, séparateur de batterie, batterie et procédé de production de film composite poreux
WO2017082542A1 (fr) Feuille de cuivre électrolytique, électrode comprenant celle-ci, batterie secondaire comprenant celle-ci, et son procédé de fabrication
WO2018088642A1 (fr) Feuille de cuivre électrolytique pour batterie secondaire et son procédé de fabrication
WO2015076571A1 (fr) Composition d'agent de revêtement de séparateur, séparateur formé de la composition d'agent de revêtement, et batterie faisant appel à celui-ci
WO2013165151A1 (fr) Séparateur et dispositif électrochimique le comprenant
JP6581219B2 (ja) リチウム二次電池用の電解銅箔及びこれを含むリチウム二次電池
WO2014208926A1 (fr) Séparateur comprenant une couche de revêtement et batterie utilisant ledit séparateur
WO2019045374A2 (fr) Feuille de cuivre électrolytique, procédé de production de celle-ci, et électrode négative de batterie secondaire au li à capacité élevée comprenant celle-ci
WO2015147419A1 (fr) Mélange d'anode de batterie rechargeable au lithium-ion, son procédé de préparation, et batterie rechargeable au lithium-ion comportant celui-ci
WO2021033795A1 (fr) Composition de revêtement de matériau bidimensionnel comprenant du graphène, séparateur de batterie l'utilisant et procédé de fabrication associé
WO2016208869A1 (fr) Feuille de cuivre électrolytique pour pile rechargeable au lithium, et pile rechargeable au lithium la comprenant
WO2018088646A1 (fr) Feuille de cuivre électrolytique pour batterie secondaire et son procédé de fabrication
WO2016204405A1 (fr) Feuille de cuivre électrolytique pour une batterie secondaire au lithium et batterie secondaire au lithium contenant ladite feuille
WO2018088644A1 (fr) Feuille de cuivre électrolytique pour batterie secondaire, ayant d'excellentes propriétés physiques à basse température, et son procédé de production
WO2019151719A1 (fr) Feuille de cuivre électrolytique douée de stabilité dimensionnelle et de stabilité de texture à hautes températures, et son procédé de fabrication
WO2023096206A1 (fr) Procédé de préparation d'un prépolymère à base d'uréthane
WO2019151718A1 (fr) Feuille de cuivre électrolytique ayant d'excellentes caractéristiques de manipulation en post-traitement et procédé de fabrication s'y rapportant
WO2023219264A1 (fr) Procédé de fabrication d'une feuille de cuivre électrolytique
WO2018088645A1 (fr) Feuille de cuivre électrolytique pour batterie secondaire ayant une excellente résistance à la flexion et son procédé de production
CN113488743B (zh) 一种锂电池正极极耳绝缘涂层及其制备方法
WO2021125410A1 (fr) Feuille de cuivre traitée en surface, son procédé de production, et électrode négative pour batterie secondaire la comprenant

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 15315774

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16811818

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017565096

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016811818

Country of ref document: EP