WO2022085371A1 - Feuille de cuivre électrolytique, électrode négative pour accumulateur au lithium-ion et accumulateur au lithium-ion - Google Patents

Feuille de cuivre électrolytique, électrode négative pour accumulateur au lithium-ion et accumulateur au lithium-ion Download PDF

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WO2022085371A1
WO2022085371A1 PCT/JP2021/035367 JP2021035367W WO2022085371A1 WO 2022085371 A1 WO2022085371 A1 WO 2022085371A1 JP 2021035367 W JP2021035367 W JP 2021035367W WO 2022085371 A1 WO2022085371 A1 WO 2022085371A1
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Prior art keywords
copper foil
electrolytic copper
electrolytic
lithium ion
ion secondary
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PCT/JP2021/035367
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English (en)
Japanese (ja)
Inventor
伸 菊池
亮二 高澤
正靖 笠原
竜介 中崎
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古河電気工業株式会社
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Priority to JP2022515789A priority Critical patent/JPWO2022085371A1/ja
Publication of WO2022085371A1 publication Critical patent/WO2022085371A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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

Definitions

  • the present invention relates to an electrolytic copper foil, a negative electrode for a lithium ion secondary battery using the electrolytic copper foil, and a lithium ion secondary battery including the negative electrode for the lithium ion secondary battery.
  • a copper foil may be used as a negative electrode current collector of a lithium ion secondary battery, but the copper foil may break due to expansion and contraction of the negative electrode material during charging and discharging of the lithium ion secondary battery.
  • the copper foil and the negative electrode material that are in close contact with each other are locally peeled off during charging and discharging, and stress during expansion and contraction is concentrated on the peeled portion, so that the copper foil may break.
  • Patent Documents 1 and 2 disclose electrolytic copper foils that can be used as a negative electrode current collector for a lithium ion secondary battery and have improved adhesion to a negative electrode material by controlling surface roughness.
  • Patent Document 3 discloses an electrolytic copper foil for a secondary battery, which can withstand expansion and contraction of a negative electrode material during charging and discharging and has excellent bending resistance.
  • Patent Document 4 discloses a technique for manufacturing a secondary battery having excellent performance by using a copper foil in which sagging, wrinkling, and tearing are suppressed by controlling surface roughness and the like. In recent years, research on lithium-ion secondary batteries has progressed, and further improvement in performance is required. Therefore, copper foils that are less likely to break during charging and discharging are required. Since the electrolytic copper foils disclosed in Patent Documents 1 to 4 may have insufficient mechanical properties and adhesion to the negative electrode material, they may be broken during charging / discharging of the lithium ion secondary battery.
  • An object of the present invention is to provide an electrolytic copper foil that is less likely to break. Another object of the present invention is to provide a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery in which the negative electrode current collector is less likely to break during charging and discharging.
  • the foil thickness is t (unit: ⁇ m), and the concave average volume, which is the average value of the volumes of the concave portions formed on the electrolytic precipitation end surface, is VAV (unit: ⁇ m 3 ). ), The elongation rate measured by pulling along the length direction is E (unit is%), and when the concave average volume VAV is measured using a white interference microscope, the foil thickness t is 10 or more and 20 or less.
  • VAV ⁇ t which is the product of the concave average volume VAV and the foil thickness t, is more than 0 and 1000 or less, and E / t obtained by dividing the elongation rate E by the foil thickness t is 0.9 or more and 1.8 or less. Is the gist.
  • the negative electrode for a lithium ion secondary battery according to another aspect of the present invention includes the electrolytic copper foil according to the above aspect. Further, it is a gist that the lithium ion secondary battery according to another aspect of the present invention includes a negative electrode for a lithium ion secondary battery according to the other aspect.
  • the electrolytic copper foil of the present invention is less likely to break. Further, the negative electrode for a lithium ion secondary battery and the lithium ion secondary battery of the present invention are less likely to break in the negative electrode current collector during charging and discharging.
  • the electrolytic copper foil according to the embodiment of the present invention has a foil thickness of t (unit: ⁇ m) and a concave average volume (Valleys Average Volume) which is an average value of the volumes of the concave portions formed on the electrolytic precipitation end surface.
  • VAV unit: ⁇ m 3
  • E unit:%
  • the foil thickness is t.
  • VAV ⁇ t which is the product of the average volume VAV of the recess and the foil thickness t, is more than 0 and 1000 or less
  • E / t obtained by dividing the elongation rate E by the foil thickness t is 0.9 or more and 1 It is 0.8 or less. Due to such a configuration, the electrolytic copper foil of the present embodiment is unlikely to break.
  • the electrolytic copper foil of the present embodiment can be used as a negative electrode current collector of a lithium ion secondary battery (mainly a cylindrical lithium ion secondary battery). That is, the negative electrode for the lithium ion secondary battery of the present embodiment includes the electrolytic copper foil of the present embodiment. Further, the lithium ion secondary battery of the present embodiment includes the negative electrode for the lithium ion secondary battery of the present embodiment. Since the electrolytic copper foil of the present embodiment is hard to break, the negative electrode for the lithium ion secondary battery and the lithium ion secondary battery of the present embodiment are hard to break in the negative electrode current collector during charging and discharging.
  • the electrolytic copper foil of the present embodiment will be described in more detail.
  • the present inventor has found that the electrolytic copper foil having both high stretchability and smoothness (low profile) of the electrolytic precipitation end surface has a negative electrode material during charging and discharging of a lithium ion secondary battery. It was found that breakage is unlikely to occur even if it expands and contracts.
  • the electrolytic copper foil has high stretchability, the electrolytic copper foil can follow the expansion and contraction of the negative electrode material, so that breakage is unlikely to occur. Further, if the concave average volume VAV, which is the average value of the volumes of the fine recesses formed on the electrolytic precipitation end surface, is small and the electrolytic precipitation end surface is smooth, the electrolytic copper foil and the negative electrode material that are in close contact with each other are used. Since the adhesion force of the metal is uniform over the entire contact surface, it is possible to prevent local peeling between the electrolytic copper foil and the negative electrode material that are in close contact with each other during charging and discharging.
  • VAV concave average volume
  • VAV which is the average value of the volumes of the fine recesses formed on the electrolytic precipitation end surface
  • the relationship between the foil thickness of the electrolytic copper foil and the elongation rate due to tension is often unclear, and even with the electrolytic copper foil of the same foil thickness, the characteristics such as the elongation rate have varied.
  • the foil thickness is increased, the tensile breakage of the electrolytic copper foil is accelerated during charging and discharging of the lithium ion secondary battery due to the change in the copper precipitation mechanism during electrolytic plating (copper plating for producing electrolytic copper foil). There was also the problem of.
  • the present inventor has found that the value obtained by normalizing the elongation rate by the foil thickness (that is, the parameter E / t) falls within a certain region by controlling the electrolytic conditions of the electrolytic plating. Then, it was found that the lithium ion secondary battery manufactured by using the electrolytic copper foil thus obtained as the negative electrode current collector is less likely to break in the negative electrode current collector during charging and discharging.
  • a smooth electrolytic copper foil having a small surface roughness such as Ra and Rz is less likely to break.
  • the surface roughness of Ra, Rz, etc. is calculated from the profile in any one line on the surface of the electrolytic copper foil, and is the size of the fine recesses existing in the region having a certain area. Etc. are numerical values that are not sufficiently expressed.
  • the present inventor has found that, during electrolytic plating, copper crystal grows in the thickness direction of the electrolytic copper foil, so that a large number of cubic micrometer-scale fine recesses are formed on the surface of the electrolytic copper foil. I found. Then, it has been found that when the volume of the concave portion is large, when the negative electrode material expands and contracts during charging and discharging of the lithium ion secondary battery, the concave portion serves as a starting point and the electrolytic copper foil is likely to break. The recess formed by this copper crystal growth may become larger in proportion to the foil thickness.
  • the present inventor reduces the average recess volume VAV, which is the average value of the volumes of the recesses formed on the end surface of electrolytic precipitation, and reduces the average volume VAV of the recesses due to the foil thickness. It has been found that an electrolytic copper foil having a high elongation rate and less likely to break can be obtained by controlling the influence on the sheet.
  • FIG. 2 is a white interference contrast microscope image showing the unevenness formed on the electrolytic precipitation end surface of the electrolytic copper foil, and the height is represented by the shade of color.
  • FIG. 3 is a diagram showing a profile of the electrolytic precipitation end surface of the electrolytic copper foil, and is a profile in one line in the white interference contrast microscope image of FIG. The portion lower than the horizontal line having a height of 0 ⁇ m set in accordance with the ISO 25178 rule is the recess formed on the electrolytic precipitation end surface.
  • the recessed average volume VAV is affected by two factors: suppressing copper crystal growth in the thickness direction of the electrolytic copper foil and increasing the foil thickness. Therefore, when estimating the degree of suppression of crystal growth from the recessed average volume VAV for electrolytic copper foils having different foil thicknesses, it is necessary to compare VAV ⁇ t, which is the product of the recessed average volume VAV and the foil thickness t. be. From the above, it was found that by defining both the parameter VAV ⁇ t and the parameter E / t, the target electrolytic copper foil that is less likely to break can be obtained.
  • the foil thickness t needs to be 10 ⁇ m or more and 20 ⁇ m or less, but is preferably 12 ⁇ m or more and 20 ⁇ m or less.
  • the organic additive in the electrolytic solution functions in order to fill the large unevenness caused by the crystal growth in the thickness direction of the electrolytic copper foil, and the organic additive in the electrolytic solution functions in the thickness direction of the electrolytic copper foil. The effect of suppressing the crystal growth of copper can be obtained.
  • the concave average volume VAV tends to be large, and tensile fracture is accelerated.
  • the probability is high.
  • the electrolysis time required for foil production becomes long, so that it is easily affected by the decomposition and consumption of organic additives, and there are places where the average volume VAV of the recesses becomes extremely large. As a result, there is an increased probability that a local decrease in elongation will occur.
  • the parameter VAV ⁇ t needs to be 0 excess 1000 or less, but is preferably 0 excess 400 or less.
  • the surface of the electrolytic copper foil is smooth, so that the adhesion between the electrolytic copper foil and the negative electrode material tends to be uniform over the entire contact surface. Therefore, local peeling between the electrolytic copper foil and the negative electrode material, which are in close contact with each other, is suppressed during charging / discharging, so that breakage is less likely to occur during charging / discharging.
  • the parameter VAV ⁇ t is within the above range, the adhesive force between the electrolytic copper foil and the negative electrode material is sufficiently exhibited, so that breakage is unlikely to occur during charging and discharging.
  • the parameter E / t needs to be 0.9 or more and 1.8 or less, but is preferably 1.2 or more and 1.7 or less, and more preferably 1.3 or more and 1.6 or less.
  • the electrolytic copper foil has a high elongation rate, so that fracture is unlikely to occur during charging and discharging.
  • the root mean square height Sq of the electrolytic precipitation end surface of the electrolytic copper foil of the present embodiment measured using a white interference microscope is preferably 0.1 ⁇ m or more and 0.4 ⁇ m or less, preferably 0.1 ⁇ m or more and 0. It is more preferably .25 ⁇ m or less.
  • the adhesion between the electrolytic copper foil and the negative electrode material tends to be higher due to the anchor effect. Further, when the root mean square height Sq of the electrolytic precipitation end surface is within the above range, the electrolytic precipitation end surface is sufficiently smooth, so that the adhesion between the electrolytic copper foil and the negative electrode material that are in close contact with each other is strong. It becomes uniform over the entire contact surface. Therefore, local peeling between the electrolytic copper foil and the negative electrode material, which are in close contact with each other, is suppressed during charging / discharging, so that fracture is less likely to occur during charging / discharging.
  • the electrolytic copper foil of the present embodiment preferably has a tensile strength of 300 MPa or more and 380 MPa or less measured by pulling along the length direction. When the tensile strength is within the above range, the electrolytic copper foil is less likely to break, and the negative electrode material has more excellent followability to expansion and contraction.
  • the tensile strength of the electrolytic copper foil is measured by pulling it along the length direction, and the "length direction" of the electrolytic copper foil in the present invention means MD (Machine Direction), for example, electrolysis.
  • MD Machine Direction
  • the copper foil is formed by plating on the surface of the rotating electrode using the rotating electrode at the time of manufacturing the copper foil, it means the rotation direction of the rotating electrode.
  • the electrolytic copper foil of the present embodiment can be used not only for the negative electrode current collector of the lithium ion secondary battery but also for other purposes.
  • the electrolytic copper foil of the present embodiment can be suitably used as a copper foil for a printed wiring board. Since the electrolytic copper foil of the present embodiment has both high stretchability and smoothness of the electrolytic precipitation end surface, it is attached to the copper foil at the time of manufacturing a printed wiring board (for example, at the time of heat pressing). Even when the resin such as the epoxy resin to be combined expands and contracts, it follows the expansion and contraction, so that it is unlikely to break.
  • the electrolytic copper foil can be produced, for example, by using an electrolytic precipitation device as shown in FIG.
  • the electrolytic precipitation device of FIG. 1 includes an insoluble electrode 12 made of titanium coated with a platinum group element or an oxide thereof, and a titanium rotating electrode 11 provided facing the insoluble electrode 12. Copper plating is performed using the electrolytic precipitation device shown in FIG. 1, copper is deposited on the surface (columnar surface) of the columnar rotary electrode 11 to form a copper foil, and the copper foil is peeled off from the surface of the rotary electrode 11. Thereby, the electrolytic copper foil of the present embodiment can be manufactured.
  • electrolytic copper is controlled by controlling conditions such as current density, electrolytic solution temperature, and electrolytic solution composition (for example, concentration of copper ions, sulfuric acid, chlorine ions, and additives in the electrolytic solution). It is possible to suppress the growth of copper crystals in the thickness direction of the foil. As a result, the electrolytic copper foil having a small concave average volume VAV, a small change in the surface texture (for example, concave average volume VAV, root mean square height Sq) due to the foil thickness of the electrolytic copper foil, and having a high elongation rate can be obtained. Obtainable.
  • an example of a method of producing an electrolytic copper foil by performing copper plating will be described in more detail with reference to FIG.
  • a current is applied using the rotating electrode 11 as a cathode and the insoluble electrode 12 as an anode.
  • the insoluble electrode 12 for example, a DSE (Dimensionally Stable Electrode) electrode (registered trademark) can be used.
  • the electrolytic solution 13 for example, an aqueous solution containing sulfuric acid and copper sulfate can be used as the electrolytic solution 13, for example.
  • the copper concentration of the electrolytic solution 13 can be, for example, 50 to 150 g / L, and the sulfuric acid concentration can be, for example, 20 to 200 g / L.
  • Additives such as organic additives and inorganic additives may be added to the electrolytic solution 13 used for copper plating from the viewpoint of smoothing the electrolytic copper foil and controlling mechanical properties. By adding the additive, the strength, elongation, and surface roughness of the electrolytic copper foil under normal conditions can be improved, and the crystal growth of copper in copper plating can be suppressed.
  • One type of additive may be used alone, or two or more types may be used in combination.
  • organic additive examples include ethylenethiourea, polyethylene glycol, and Janus Green.
  • metal chloride such as sodium chloride (NaCl) or hydrogen chloride (HCl) can be used as a source of chloride ions.
  • chloride ion chloride ion
  • ethylenethiourea polyethylene glycol and Janus Green
  • copper crystals may grow in the thickness direction of the electrolytic copper foil, but at least one of ethylenethiourea, polyethylene glycol and yanus green is added to the electrolytic solution 13 at a concentration in the above range. Then, the effect of suppressing the crystal growth of copper in the thickness direction of the electrolytic copper foil becomes large.
  • the electrolytic conditions in copper plating can be, for example, as follows. That is, the liquid temperature of the electrolytic solution 13 is 45 to 65 ° C., and the current density is 25 to 50 A / dm 2 . At the time of copper plating, the temperature of the electrolytic solution 13 may rise due to the resistance heat generation of the anode and the cathode, and the organic additive may be decomposed. Therefore, it is preferable to suppress the current density to the above-mentioned low value.
  • the surface of the electrolytic copper foil produced as described above may be surface-treated.
  • the surface treatment will be described below.
  • the surface of the electrolytic copper foil may be subjected to a rust preventive treatment.
  • the rust preventive treatment include an inorganic rust preventive treatment and an organic rust preventive treatment.
  • the inorganic rust preventive treatment include chromate treatment and plating treatment, and chromate treatment may be applied to the plating layer by the plating treatment.
  • the plating treatment include nickel plating, nickel alloy plating, cobalt plating, cobalt alloy plating, zinc plating, zinc alloy plating, tin plating, and tin alloy plating.
  • the organic rust preventive treatment include surface treatment using benzotriazole.
  • the surface that has been subjected to the rust preventive treatment may be further subjected to surface treatment (silane treatment) using a silane coupling agent.
  • silane treatment silane treatment
  • a functional group having a strong affinity with an adhesive is imparted to the surface of the electrolytic copper foil (the surface on the bonding side with the negative electrode material or the resin), so that the electrolytic copper foil and the negative electrode material are provided. Adhesion with the resin and the resin is further improved, and the rust resistance and moisture absorption heat resistance of the electrolytic copper foil are further improved. Therefore, such an electrolytic copper foil is suitable as an electrolytic copper foil for a negative electrode current collector of a lithium ion secondary battery or a printed wiring board.
  • the rust preventive treatment and the silane coupling agent treatment increase the adhesion strength between the active material of the lithium ion secondary battery and the electrolytic copper foil, and play a role of preventing deterioration of the charge / discharge cycle characteristics of the lithium ion secondary battery.
  • the surface of the electrolytic copper foil may be roughened before the above-mentioned rust preventive treatment is applied.
  • a plating method, an etching method, or the like can be preferably adopted.
  • the plating method is a method of roughening the surface by forming a thin film layer having irregularities on the surface of the untreated electrolytic copper foil. Examples of the plating method include an electrolytic plating method and an electroless plating method.
  • the roughening treatment by the plating method for example, a method of forming a plating film containing copper as a main component such as copper or a copper alloy on the surface of an untreated electrolytic copper foil is preferable.
  • a method by physical etching or chemical etching is preferable. Examples of the physical etching include a method of etching by sandblasting and the like, and examples of the chemical etching include etching performed by using a treatment liquid containing an inorganic acid or an organic acid, an oxidizing agent and an additive.
  • Example ⁇ Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
  • the electrolytic copper foils of Examples 1 to 19 and Comparative Examples 1 and 2 are manufactured, negative electrode current collectors are manufactured using these electrolytic copper foils, and a lithium ion secondary battery is manufactured using these negative electrode current collectors.
  • a lithium ion secondary battery was manufactured using these negative electrode current collectors.
  • various characteristics of the electrolytic copper foil and the lithium ion secondary battery were evaluated.
  • a method for manufacturing an electrolytic copper foil and a lithium ion secondary battery and a method for evaluating various characteristics will be described.
  • An aqueous solution containing sulfuric acid, copper sulfate pentahydrate, and additives was used as the electrolytic solution.
  • additives ethylene thiourea, polyethylene glycol, and Janus Green were used.
  • Table 1 shows the concentrations of sulfuric acid, copper sulfate pentahydrate, and each additive.
  • the concentration of copper sulfate pentahydrate is the concentration as copper.
  • Table 1 shows the chlorine concentration in the electrolytic solution.
  • the positive electrode material paste was prepared by kneading. This positive electrode material paste was uniformly applied onto the aluminum foil with a thickness of 15 ⁇ m.
  • the aluminum foil coated with the positive electrode material paste was dried in a nitrogen atmosphere to volatilize the solvent, and then roll-rolled to prepare a sheet having an overall thickness of 150 ⁇ m. After cutting this sheet into a strip having a width of 43 mm and a length of 285 mm, a lead terminal of aluminum foil was attached to one end thereof by ultrasonic welding to obtain a positive electrode.
  • the negative electrode material paste was applied to both sides of the negative electrode current collector in a double stripe shape.
  • the width of the coating film of the linear negative electrode material paste was 300 mm, and the direction in which the coating film of the linear negative electrode material paste was stretched was made parallel to the longitudinal direction of the strip-shaped negative electrode current collector.
  • the negative electrode current collector coated with the negative electrode material paste was dried in a nitrogen atmosphere to volatilize the solvent, and then roll-rolled to prepare a sheet having an overall thickness of 150 ⁇ m. After cutting this sheet into a rectangular shape having a width of 43 mm and a length of 280 mm, a nickel foil lead terminal was attached to one end thereof by ultrasonic welding to form a negative electrode.
  • (D) Preparation of Lithium Ion Secondary Battery A polypropylene separator having a thickness of 25 ⁇ m was sandwiched between the positive electrode and the negative electrode manufactured as described above, and the whole of these was wound to obtain a wound body.
  • the wound body was housed in a cylindrical battery can, and the lead terminal of the negative electrode was spot welded to the bottom of the battery can.
  • the battery can is made of mild steel whose surface is nickel-plated.
  • the top lid made of insulating material was placed on the battery can, and after inserting the gasket, the lead terminal of the positive electrode and the safety valve made of aluminum were ultrasonically welded and connected. Then, after injecting a non-aqueous electrolyte solution consisting of propylene carbonate, diethyl carbonate, and ethylene carbonate into the battery can, a lid is attached to the safety valve, and a cylindrical sealed structure lithium ion battery with an outer diameter of 14 mm and a height of 50 mm is attached. I assembled the next battery.
  • each electrolytic copper foil manufactured in the above item (A) and each lithium ion secondary battery manufactured in the above item (D) were evaluated.
  • the evaluation method will be described below.
  • the foil thickness of each electrolytic copper foil produced in the above item (A) is as shown in Table 2.
  • the surface shape was measured at any 5 points on the end surface of the electrolytic precipitation, and shape analysis was performed at each of the 5 points to obtain the concave average volume VAV and the root mean square height Sq at each of the 5 points. Then, the average value of the results of the obtained five points was taken as the concave average volume VAV and the root mean square root height Sq of the electrolytic precipitation end surface of the electrolytic copper foil.
  • the shape analysis was performed by the VSI measurement method (vertical scanning interferometry) using a high resolution CCD camera (resolution 1280 x 960 pixels).
  • the conditions are that the light source is white light, the measurement magnification is 10 times, the measurement range is 477 ⁇ m ⁇ 357.8 ⁇ m, the threshold is 3%, and the filters are Terms Removal (Cylinder and Tilt) and Data Restore (Metado: legacy, iterations 5). After that, the Foiler Filter process was performed.
  • the concave average volume VAV was determined by Multiple Region Analysis. More specifically, "Region Finding Route” is By, Thrashold (s) is 0.5 ⁇ m, Minimum Resolution size is 100 pixels, Region Level is Valleys, Zero Level is Automatic, and Term Revolve is No. The value displayed in "Avg:” was adopted as the concave average volume VAV. Since Region Level is Valley and is calculated as a negative value, the calculated concave average volume VAV is corrected by an absolute value. The root mean square height Sq was calculated using S-parameters-height analysis with Remove Til as True. Table 2 shows the measurement results of the concave average volume VAV and the root mean square height Sq.
  • the electrolytic copper foil was cut into a rectangular shape having a width of 13.0 mm and a length of 152 mm, and this was used as a measurement sample. Then, a tensile test of the measurement sample was performed using a tensile tester 1122 manufactured by Instron, and the elongation rate and the tensile strength under normal conditions were measured. In this tensile test, the distance between chucks was 70 mm, the tensile speed was 50 mm / min, and other conditions were set based on the method specified in IPC-TM-650. The results are shown in Table 2.
  • the "normal state” means a state in which the electrolytic copper foil is placed at room temperature and humidity (for example, temperature 23 ⁇ 2 ° C., humidity 50 ⁇ 5% RH).
  • an electrolytic copper foil that breaks in less than 300 cycles is not suitable for use as a negative electrode current collector. It can be said that the electrolytic copper foil that breaks in 300 cycles or more and less than 500 cycles is suitable for the use of a negative electrode current collector. The electrolytic copper foil that does not break even after 500 cycles is particularly suitable for the use of the negative electrode current collector, and can improve the charge / discharge cycle characteristics of the lithium ion secondary battery.
  • the electrolytic copper foil has a foil thickness t of 10 or more and 20 or less, and VAV ⁇ t. Since it is more than 0 and 1000 or less and the E / t is 0.9 or more and 1.8 or less, the electrolytic copper foil is less likely to break even after repeated charging and discharging, and the charge and discharge cycle characteristics of the lithium ion secondary battery are excellent. Was there.

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Abstract

La présente invention concerne une feuille de cuivre électrolytique qui n'est pas susceptible de se rompre. Dans cette feuille de cuivre électrolytique, où t est l'épaisseur de feuille (en unités de µm), VAV est le volume moyen d'évidement (en unités de µm3), qui est la valeur moyenne du volume d'évidements formés dans une surface à dépôt électrolytique achevé, E est l'allongement (en unités de %) mesuré par traction le long d'une direction de longueur, et le volume moyen d'évidement VAV est mesuré à l'aide d'un microscope à interférence blanche, l'épaisseur de feuille t est de 10 à 20, le produit VAV × t du volume moyen d'évidement VAV et de l'épaisseur de feuille t est supérieur à 0 et au maximum de 1000, et le quotient E/t de l'allongement E divisé par l'épaisseur de feuille t est de 0,9 à 1,8.
PCT/JP2021/035367 2020-10-22 2021-09-27 Feuille de cuivre électrolytique, électrode négative pour accumulateur au lithium-ion et accumulateur au lithium-ion WO2022085371A1 (fr)

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Citations (6)

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JP2004263289A (ja) * 2002-10-25 2004-09-24 Fukuda Metal Foil & Powder Co Ltd 低粗面電解銅箔及びその製造方法
JP2018014332A (ja) * 2015-10-15 2018-01-25 長春石油化學股▲分▼有限公司 耐たるみ性を示す銅箔
WO2019163962A1 (fr) * 2018-02-23 2019-08-29 古河電気工業株式会社 Feuille de cuivre électrolytique, électrode négative d'élément secondaire au lithium-ion utilisant la feuille de cuivre électrolytique, élément secondaire au lithium-ion, stratifié à placage de cuivre et carte de circuit imprimé
JP2020125540A (ja) * 2019-02-01 2020-08-20 長春石油化學股▲分▼有限公司 リチウムイオン二次電池の負極集電体に用いられる銅箔
JP2020147844A (ja) * 2019-03-14 2020-09-17 長春石油化學股▲分▼有限公司 抗銅バリ特性を有する電解銅箔

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JP2004162144A (ja) * 2002-11-15 2004-06-10 Nippon Denkai Kk 電解銅箔の製造方法
JP2018014332A (ja) * 2015-10-15 2018-01-25 長春石油化學股▲分▼有限公司 耐たるみ性を示す銅箔
WO2019163962A1 (fr) * 2018-02-23 2019-08-29 古河電気工業株式会社 Feuille de cuivre électrolytique, électrode négative d'élément secondaire au lithium-ion utilisant la feuille de cuivre électrolytique, élément secondaire au lithium-ion, stratifié à placage de cuivre et carte de circuit imprimé
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JP2020147844A (ja) * 2019-03-14 2020-09-17 長春石油化學股▲分▼有限公司 抗銅バリ特性を有する電解銅箔

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