WO2013146369A1 - Aluminum alloy foil for electrode current collector and method for manufacturing same - Google Patents
Aluminum alloy foil for electrode current collector and method for manufacturing same Download PDFInfo
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- WO2013146369A1 WO2013146369A1 PCT/JP2013/057474 JP2013057474W WO2013146369A1 WO 2013146369 A1 WO2013146369 A1 WO 2013146369A1 JP 2013057474 W JP2013057474 W JP 2013057474W WO 2013146369 A1 WO2013146369 A1 WO 2013146369A1
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- aluminum alloy
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- alloy foil
- heat treatment
- mpa
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- 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 aluminum alloy foil for an electrode current collector of a positive electrode material or a negative electrode material of an electricity storage device such as a lithium ion secondary battery, and a method for producing the same.
- Lithium ion secondary batteries are superior to lead batteries and nickel metal hydride batteries in terms of weight and energy density per volume, and can reduce the weight and size of installed devices. Therefore, in recent years, it is actively used as a power source not only for portable electronic devices but also for electric vehicles (EV), hybrid electric vehicles (HEV), etc., and it is expected that the demand will further increase in the future.
- EV electric vehicles
- HEV hybrid electric vehicles
- a lithium ion secondary battery is a battery that is charged and discharged by a reaction in which lithium ions move between a positive electrode and a negative electrode, and has a three-layer structure of a positive electrode, a separator, and a negative electrode.
- Lithium transition metal composite oxides such as lithium cobaltate, lithium nickelate, and lithium manganate are mainly used for the positive electrode active material
- carbon-based materials such as graphite, soft carbon, and hard carbon are mainly used for the negative electrode active material.
- a polymer porous membrane is used for the separator that separates the positive electrode and the negative electrode, and a non-aqueous solvent is used for the electrolyte.
- the positive electrode of a lithium ion secondary battery is generally manufactured as follows. First, a paste obtained by dispersing or dissolving an active material (LiCoO 2 or the like), a conductive aid (carbon black or the like), a binder (polytetrafluoroethylene or the like), a thickener (polyvinylidene fluoride or the like) in a solvent, and kneading. To prepare. After applying this paste to the aluminum alloy foil serving as the current collector (hereinafter, the process of “applying the paste to the aluminum alloy foil serving as the current collector” is referred to as the active material coating process), the solvent is dried and the positive electrode A composite layer is formed.
- an active material LiCoO 2 or the like
- a conductive aid carbon black or the like
- a binder polytetrafluoroethylene or the like
- a thickener polyvinylidene fluoride or the like
- press process a compression process is performed by a press machine (hereinafter, the process of “compressing by a press machine” is referred to as press process).
- press process The positive electrode material manufactured in this way is laminated with the separator and the negative electrode material, and then wound, molded for storage in the case, and then stored in the case.
- the aluminum alloy foil is required to have a certain strength. If the strength of the aluminum alloy foil is insufficient, defects such as deformation and cutting are likely to occur in the active material application process.
- lithium ion secondary batteries may be used in applications that require large currents such as automobiles and power tools.
- the conductivity of the aluminum alloy foil for the current collector is low, the battery There is a problem that the internal resistance increases and the output voltage decreases.
- the aluminum alloy foil is required to have both high strength and high conductivity.
- elements such as Si, Fe, Mn, and Cu may be added.
- foil rolling is performed by adding such an element.
- cuts are likely to occur or the conductivity is lowered.
- a high-purity aluminum alloy not containing the above elements does not have sufficient strength.
- heat treatment at about 100 ° C. to 180 ° C. is performed, so the strength after the drying process tends to be lower than the strength of the base plate. . If the strength after this drying process is too low, medium elongation is likely to occur during press processing, so that wrinkles are generated during winding, the adhesiveness between the active material and the aluminum alloy foil is reduced, and breakage during slitting Is likely to occur. When the adhesion between the active material and the surface of the aluminum alloy foil is lowered, there is a problem in that peeling progresses during repeated use of charge and discharge and the capacity of the battery is reduced. At present, heat treatment at around 150 ° C. is the mainstream as the drying process, but in order to improve the efficiency of the drying process, there is a demand for an aluminum alloy foil that can maintain sufficient strength even in a higher temperature range such as 180 ° C.
- Patent Document 1 proposes an aluminum alloy foil for an electrode current collector in which the tensile strength of the base plate is 98 MPa or more. However, it cannot be said that the strength is sufficient to prevent the occurrence of breakage during the manufacturing process, and there is no description regarding the electrical conductivity.
- Patent Documents 2 and 3 propose aluminum alloy foils for battery electrode current collectors, in which the tensile strength of the base plate is 200 MPa or more, but are alloys with addition of Mn, Mg, etc. as main elements. Therefore, high electrical conductivity cannot be satisfied.
- Patent Document 4 proposes an aluminum alloy foil for a lithium ion battery electrode current collector, in which the tensile strength of the base plate is 160 MPa or more. However, the strength after heat treatment assuming a drying process is low, and it cannot be said to be sufficient to prevent medium elongation during press working.
- an aluminum alloy foil for an electrode current collector having good characteristics in both strength and conductivity could not be obtained.
- This invention is made
- An object of the present invention is to provide an aluminum alloy foil.
- the inventors of the present invention have studied aluminum alloy foil used for the positive electrode material of a lithium ion secondary battery.
- the components are controlled within an appropriate range, and the manufacturing process is performed without a high-temperature and long-time heat treatment.
- Fe 0.1 to 0.5 mass% (hereinafter simply referred to as%), Si: 0.01 to 0.3%, Cu: 0.01 to 0.2%, Mn : 0.01% or less, balance Al and inevitable impurities, tensile strength 230 MPa or more, 0.2% proof stress 190 MPa or more, conductivity 55% IACS or more, 180 ° C. for 1 hour
- An aluminum alloy foil for an electrode current collector having a tensile strength after heat treatment of 160 MPa or more and a 0.2% proof stress of 140 MPa or more when the above heat treatment is performed.
- a second invention is a method for producing an aluminum alloy foil for an electrode current collector as described above, wherein Fe: 0.1 to 0.5%, Si: 0.01 to 0.3%, Cu: 0.00.
- Heat treatment under conditions satisfying the following formula (1) or (2) for an aluminum alloy ingot containing 01 to 0.2%, Mn: 0.01% or less and the balance being Al and inevitable impurities
- Electrode collector characterized in that the steel sheet is warm-rolled at a start temperature of 150 to 390 ° C. and an end temperature of 150 to 300 ° C., and cold rolling and foil rolling are sequentially performed without intermediate annealing. It is a manufacturing method of the aluminum alloy foil for bodies.
- the strength of the base plate and the strength after the drying process are high, so that it is possible to prevent the occurrence of cuts in the active material coating process and the middle elongation during press processing. It is possible to provide an aluminum alloy foil that is most suitable for an aluminum alloy foil for an electrode current collector, such as an aluminum alloy foil for a lithium ion battery.
- composition of the aluminum alloy foil for lithium ion batteries according to the present invention is as follows: Fe: 0.1 to 0.5%, Si: 0.01 to 0.3%, Cu: 0.01 to 0.2%, Mn: It contains 0.01% or less, and consists of the balance Al and inevitable impurities.
- Fe is an element that improves the strength when added, and is contained in an amount of 0.1 to 0.5%. If the added amount of Fe is less than 0.1%, the strength is not improved. On the other hand, if the amount of Fe exceeds 0.5%, a large amount of Al—Fe compound or Al—Fe—Si compound is present inside and on the surface of the aluminum alloy foil, which is not preferable because pinholes are increased.
- Si is an element that improves the strength when added, and is contained in an amount of 0.01 to 0.3%. If the amount of Si added is less than 0.01%, the strength is not improved.
- the Al bullion used normally contains Si as an impurity, and high purity bullion is used to regulate to less than 0.01%. is there.
- the amount of Si added exceeds 0.3%, the work hardenability becomes high, so that cutting during foil rolling tends to occur, and the Al—Fe—Si compound is formed inside and on the surface of the aluminum alloy foil. This is not preferable because it increases the number of pinholes.
- Cu is an element that improves the strength when added, and is contained in an amount of 0.01 to 0.2%. If the amount of Cu added is less than 0.01%, the strength decreases. On the other hand, if the amount of Cu added exceeds 0.2%, the work curability becomes high, so that breakage during foil rolling is likely to occur.
- Mn When Mn is contained even in a small amount, Mn is regulated to 0.01% or less in order to greatly reduce the conductivity. If it exceeds 0.01%, it is difficult to maintain high conductivity, which is not preferable.
- this material contains inevitable impurities such as Cr, Ni, Zn, Mg, Ti, B, V, and Zr. These inevitable impurities are preferably 0.02% or less individually, and the total amount is preferably 0.15% or less.
- the base metal tensile strength of the aluminum alloy foil for electrode current collector according to the present invention is 230 MPa or more, and the 0.2% proof stress is 190 MPa or more. If the tensile strength is less than 230 MPa and the 0.2% proof stress is less than 190 MPa, the strength is insufficient, and breakage is likely to occur due to the tension applied during application of the active material. In addition, it also causes problems such as medium elongation, which adversely affects productivity.
- the manufacturing process of the positive electrode material includes a drying process after applying the active material for the purpose of removing the solvent in the active material.
- heat treatment is performed at a temperature of about 100 to 180 ° C.
- This heat treatment may soften the aluminum alloy foil and change its mechanical properties, so the mechanical properties of the aluminum alloy foil after the heat treatment become important.
- heat treatment is often performed at around 150 ° C., but in order to improve productivity, an aluminum alloy foil capable of maintaining sufficient strength even in a higher temperature range is demanded. In the present invention, even when heat treatment is performed at 180 ° C.
- the production conditions are appropriately controlled so that the tensile strength after heat treatment is 160 MPa or more and the 0.2% proof stress is 140 MPa or more. If the tensile strength after heat treatment is less than 160 MPa and the 0.2% proof stress is less than 140 MPa, medium elongation is likely to occur during press processing after the drying step, so that wrinkles are generated during winding and the active material is peeled off. And breakage during slitting is likely to occur, which is not preferable.
- the conductivity is 55% IACS or higher.
- the conductivity indicates the solid solution state of the solute element.
- the electrode collector of the present application is used for a lithium ion secondary battery, if the electrical conductivity is less than 55% IACS, the battery capacity is reduced when used at a high current value such that the discharge rate exceeds 5C, which is not preferable.
- 1 C is a current value at which discharge is completed in one hour after a constant current discharge is performed on a cell having a nominal capacity value.
- an aluminum alloy ingot having the above alloy composition is produced by the following steps.
- An aluminum alloy having the above composition is melted in accordance with a conventional method, and a normal casting method such as a continuous casting method or a semi-continuous casting method (DC casting method) is appropriately selected and cast.
- a normal casting method such as a continuous casting method or a semi-continuous casting method (DC casting method) is appropriately selected and cast.
- the cast aluminum alloy ingot is warm-rolled at a starting temperature of 150 to 390 ° C. without performing heat treatment under conditions satisfying the following formula (1) or (2).
- the cast aluminum alloy ingot is subjected to (a) heat treatment at less than 400 ° C. or (b) comparison satisfying t ⁇ 0.0004T 2 ⁇ 0.4T + 101 at 400 ° C. to 500 ° C. After heat treatment for a short time, warm rolling is performed at a starting temperature of 150 to 390 ° C.
- the strength of the base plate and the strength after the drying process may be reduced.
- the upper limit of the warm rolling start temperature is preferably 300 ° C., more preferably 250 ° C.
- the lower limit of the warm rolling start temperature is set to 150 ° C. In the case where productivity is more important, the lower limit temperature is preferably 200 ° C., more preferably 245 ° C.
- the end temperature of warm rolling is preferably 150 to 300 ° C.
- the end temperature at the time of warm rolling can be determined by changing the line speed and adjusting the processing heat generation and cooling conditions.
- the warm-rolled aluminum plate is wound up on the exit side of the warm rolling mill to be cooled as a coil.
- the lower limit of the end temperature is preferably 200 ° C. when productivity is more important, and is preferably 250 ° C. when more importance is attached.
- the end temperature of warm rolling exceeds 300 ° C., recrystallization proceeds during coil cooling, so that the dislocation density decreases and the strength decreases.
- a heat treatment is required for causing the aluminum alloy ingot to reach a predetermined warm rolling start temperature.
- this heat treatment as shown in the following (1) to (4), a process including one or more steps combining heating, cooling by forced cooling represented by fan air cooling and water cooling or natural cooling is considered. It is done.
- Heat treatment 1-step process example [Heating] ⁇ Warm rolling
- Heat treatment 2-step process example [heating ⁇ cooling] ⁇ Warm rolling
- Heat treatment 2-step process example [Heating ⁇ higher temperature (re) heating] ⁇ Warm rolling
- Heat treatment 3-step process Example [Heating ⁇ Cooling ⁇ (Re) heating] ⁇ Warm rolling
- Step (1) is an example of a process in which warm rolling is started when the aluminum alloy ingot is heated to 150 to 390 ° C. without heating and actively cooling the aluminum alloy ingot.
- the aluminum alloy is heated to 150 to 390 ° C. by an intended aggressive cooling process such as forced cooling or natural cooling.
- step (3) the aluminum alloy ingot is heated under conditions that do not satisfy the above expressions (1) and (2), and then at the start temperature of warm rolling.
- step (3) is a step of reheating to 150 to 390 ° C. and starting warm rolling.
- step (4) the aluminum alloy ingot is heated under conditions that do not satisfy the expressions (1) and (2).
- Forced cooling or natural cooling Was cooled by the intended active cooling step, upon reaching a subsequent 0.99 ⁇ 390 ° C. suitable for warm rolling by reheating, is a step to start a warm rolling.
- Heating under conditions that do not satisfy the expressions (1) and (2) means (a) heating at a temperature lower than 400 ° C., or (b) 400 ° C. or higher and 500 ° C. or lower, and t It means heating in a relatively short time that satisfies ⁇ 0.0004T 2 ⁇ 0.4T + 101 (T is the heating temperature (° C.), and t is the holding time (hour)).
- the heating temperature and holding time of heating and reheating performed after casting to the start of warm rolling are in a range not satisfying the above formulas (1) and (2), and the strength of the base plate and the strength after the drying step are further increased.
- the upper limit of the heating and reheating temperature when emphasizing is preferably 300 ° C, more preferably 250 ° C.
- the heating temperature is less than 400 ° C.
- the upper limit of the holding time is preferably within 24 hours.
- the aluminum alloy ingot has reached a predetermined temperature, there is no need to perform holding, and therefore there is no particular lower limit for the holding time.
- the heating temperature in the first step is 50 ° C.
- the lower limit of the final heating step is limited to 150 ° C. due to the restriction of the warm rolling start temperature.
- the heat treatment is not particularly problematic in terms of material characteristics even if it is a process of two or more steps as shown in the steps (2) to (4), but causes an increase in cost or a decrease in productivity due to an increase in the number of manufacturing steps. Therefore, the one-step process shown in the process (1) is preferable.
- ⁇ Cold rolling and foil rolling are performed after the warm rolling is completed, but intermediate annealing is not performed before or during the cold rolling and foil rolling.
- intermediate annealing is performed, the dislocation density introduced by rolling before the intermediate annealing is reduced, and the strength is reduced.
- the thickness of the aluminum alloy foil after the final foil rolling is preferably 5 to 30 ⁇ m. When the thickness is less than 5 ⁇ m, pinholes are likely to occur during foil rolling. On the other hand, when it exceeds 30 ⁇ m, the volume and weight of the electrode current collector closed to the same volume increase, and the volume and weight of the active material decrease. This is not preferable because the battery capacity of the lithium ion secondary battery is reduced.
- An aluminum alloy having the composition shown in Table 2 was melt cast by a semi-continuous casting method to produce an ingot having a thickness of 800 mm.
- heat treatment, warm or hot rolling was performed under the conditions shown in Table 3, and the plate thickness was set to 3.0 mm.
- cold rolling and foil rolling were performed to obtain an aluminum alloy foil having a foil thickness of 12 ⁇ m.
- intermediate annealing was performed at 400 ° C. for 3 hours. After the intermediate annealing, cold rolling and foil rolling were performed in the same manner as the material that was not subjected to the intermediate annealing to obtain an aluminum alloy foil having a foil thickness of 12 ⁇ m.
- Table 3 also describes the presence or absence of active cooling and reheating during heat treatment and the conditions.
- the positive cooling was performed under two conditions: forced air cooling using a fan for the ingot after heating and cooling by allowing the ingot after heating to stand to cool at room temperature.
- a positive electrode material for a lithium ion secondary battery was manufactured from each aluminum alloy foil having a foil thickness of 12 ⁇ m prepared by the method described above.
- Polyvinylidene fluoride (PVDF) serving as a binder was added to an active material mainly composed of LiCoO 2 to form a positive electrode slurry.
- PVDF polyvinylidene fluoride
- a positive electrode slurry was applied to both surfaces of the aluminum alloy foil having a width of 30 mm, heat-treated at 180 ° C. for 1 hour and dried, and then subjected to compression with a roller press to obtain a positive electrode material sample.
- coating process and the presence or absence of active material peeling were evaluated. The results are shown in Table 4.
- Table 4 also describes the rolling properties of warm and hot rolling. The case where the maximum rolling reduction in one pass of warm or hot rolling was 40% or more was marked with ⁇ , and the case where it was less than 40% was marked with ⁇ .
- ⁇ Tensile strength and 0.2% yield strength> The tensile strength and 0.2% proof stress of the aluminum alloy foil cut in the rolling direction were measured using an Instron type tensile tester AG-10kNX manufactured by Shimadzu Corporation. The measurement conditions were a test piece size of 10 mm ⁇ 100 mm, a distance between chucks of 50 mm, and a crosshead speed of 10 mm / min. In addition, assuming the drying step, the aluminum alloy foil after heat treatment at 180 ° C. for 1 hour was cut in the rolling direction, and the tensile strength and 0.2% proof stress were measured in the same manner as described above.
- the electrical conductivity was determined by measuring the electrical resistivity value by the four probe method and converting it to electrical conductivity.
- ⁇ Pinhole density> The aluminum alloy foil rolled to 12 ⁇ m was coiled with a width of 0.6 m and a length of 6000 m, and the number of pinholes was measured with a surface inspection machine. By dividing the measured number of pinholes by the total surface area, the number of pinholes per 1 m 2 of unit area was calculated and used as the pinhole density.
- Comparative Example 39 in which the Fe amount deviated from the upper limit specified in the present invention, the conductivity was low and many pinholes were generated.
- Comparative Example 40 in which the Fe amount was outside the lower limit defined in the present invention, the base plate strength and the strength after heat treatment at 180 ° C. for 1 hour were insufficient, so Peeling occurred.
- Comparative Example 42 In Comparative Example 42 in which the amount of Cu deviated from the upper limit specified in the present invention, the work hardenability was too high, and breakage occurred during foil rolling. On the other hand, in Comparative Example 43 in which the Cu amount deviated from the lower limit specified in the present invention, the base plate strength and the strength after heat treatment at 180 ° C. for 1 hour were insufficient, so Peeling occurred.
- Comparative Example 45 in which the warm rolling start temperature deviates from the upper limit specified in the present invention
- Comparative Examples 46 to 49 in which the heat treatment conditions deviate from the upper limit defined in the present invention, both the heat treatment temperature and the warm rolling start temperature are in the present invention
- Comparative Examples 50 to 51 which deviated from the upper limit specified in (1)
- the strength of the base plate and the strength after heat treatment at 180 ° C. for 1 hour were insufficient, and the active material coating process was broken and the active material was peeled off.
- Comparative Example 52 in which the end temperature of the warm rolling is outside the upper limit of the temperature range defined in the present invention, the base plate strength and the strength after heat treatment at 180 ° C.
- Comparative Example 53 in which the intermediate annealing was performed, the base plate strength and the strength after heat treatment at 180 ° C. for 1 hour were insufficient, and breakage and peeling of the active material occurred in the active material coating process.
- Comparative Example 54 in which the warm rolling start temperature deviated from the lower limit specified in the present invention, the rolling performance deteriorated because the rolling reduction of one pass during the warm rolling decreased.
Abstract
Description
T>500 (1)
500≧T≧400 かつ t≧0.0004T2-0.4T+101 (2)
(Tは、加熱温度(℃)であり、tは、保持時間(時間)である。) A second invention is a method for producing an aluminum alloy foil for an electrode current collector as described above, wherein Fe: 0.1 to 0.5%, Si: 0.01 to 0.3%, Cu: 0.00. Heat treatment under conditions satisfying the following formula (1) or (2) for an aluminum alloy ingot containing 01 to 0.2%, Mn: 0.01% or less and the balance being Al and inevitable impurities Electrode collector, characterized in that the steel sheet is warm-rolled at a start temperature of 150 to 390 ° C. and an end temperature of 150 to 300 ° C., and cold rolling and foil rolling are sequentially performed without intermediate annealing. It is a manufacturing method of the aluminum alloy foil for bodies.
T> 500 (1)
500 ≧ T ≧ 400 and t ≧ 0.0004T 2 −0.4T + 101 (2)
(T is the heating temperature (° C.), and t is the holding time (hours).)
本発明に係るリチウムイオン電池用アルミニウム合金箔の組成は、Fe:0.1~0.5%、Si:0.01~0.3%、Cu:0.01~0.2%、Mn:0.01%以下を含有し、残部Al及び不可避的不純物からなる。 <Composition of aluminum alloy foil>
The composition of the aluminum alloy foil for lithium ion batteries according to the present invention is as follows: Fe: 0.1 to 0.5%, Si: 0.01 to 0.3%, Cu: 0.01 to 0.2%, Mn: It contains 0.01% or less, and consists of the balance Al and inevitable impurities.
本発明に係る電極集電体用アルミニウム合金箔の素板引張強さは230MPa以上、0.2%耐力は190MPa以上とする。引張強さが230MPa未満、0.2%耐力が190MPa未満では強度が不足し、活物質塗布時に加わる張力によって、切れが発生し易くなる。また、中伸びなどの不具合も引き起こし、生産性に悪影響を及ぼすため、好ましくない。 <Strength of base plate>
The base metal tensile strength of the aluminum alloy foil for electrode current collector according to the present invention is 230 MPa or more, and the 0.2% proof stress is 190 MPa or more. If the tensile strength is less than 230 MPa and the 0.2% proof stress is less than 190 MPa, the strength is insufficient, and breakage is likely to occur due to the tension applied during application of the active material. In addition, it also causes problems such as medium elongation, which adversely affects productivity.
正極材の製造工程は、活物質中の溶媒を除去する目的で活物質塗布後に乾燥工程がある。この乾燥工程では100~180℃程度の温度の熱処理が行われる。この熱処理により、アルミニウム合金箔は軟化して機械的特性が変化する場合があるため、熱処理後のアルミニウム合金箔の機械的特性が重要となる。現状の乾燥工程では150℃前後で熱処理される場合が多いが、生産性を向上させるためより高温域でも十分な強度を維持可能なアルミニウム合金箔が求められている。本発明では、180℃で1時間の熱処理を行った場合でも熱処理後の引張強さが160MPa以上、0.2%耐力が140MPa以上となるように製造条件を適切に制御する。この熱処理後の引張強さが160MPa未満、0.2%耐力が140MPa未満では、乾燥工程後のプレス加工時に中伸びが発生し易くなるため、捲回時に捲きしわが発生し、活物質の剥離やスリット時の破断が起こり易くなるため、好ましくない。 <Strength after heat treatment>
The manufacturing process of the positive electrode material includes a drying process after applying the active material for the purpose of removing the solvent in the active material. In this drying step, heat treatment is performed at a temperature of about 100 to 180 ° C. This heat treatment may soften the aluminum alloy foil and change its mechanical properties, so the mechanical properties of the aluminum alloy foil after the heat treatment become important. In the current drying process, heat treatment is often performed at around 150 ° C., but in order to improve productivity, an aluminum alloy foil capable of maintaining sufficient strength even in a higher temperature range is demanded. In the present invention, even when heat treatment is performed at 180 ° C. for 1 hour, the production conditions are appropriately controlled so that the tensile strength after heat treatment is 160 MPa or more and the 0.2% proof stress is 140 MPa or more. If the tensile strength after heat treatment is less than 160 MPa and the 0.2% proof stress is less than 140 MPa, medium elongation is likely to occur during press processing after the drying step, so that wrinkles are generated during winding and the active material is peeled off. And breakage during slitting is likely to occur, which is not preferable.
導電率は55%IACS以上とする。導電率は溶質元素の固溶状態を示す。本願電極集電体をリチウムイオン二次電池に用いる場合、導電率が55%IACS未満では、放電レートが5Cを超えるような高い電流値で使用する際に、電池容量が低下するため、好ましくない。なお、1Cとは公称容量値の容量を有するセルを定電流放電して、1時間で放電終了となる電流値のことである。 <Conductivity>
The conductivity is 55% IACS or higher. The conductivity indicates the solid solution state of the solute element. When the electrode collector of the present application is used for a lithium ion secondary battery, if the electrical conductivity is less than 55% IACS, the battery capacity is reduced when used at a high current value such that the discharge rate exceeds 5C, which is not preferable. . Note that 1 C is a current value at which discharge is completed in one hour after a constant current discharge is performed on a cell having a nominal capacity value.
本発明では上記合金組成のアルミニウム合金鋳塊を以下の工程で製造する。
前記組成を有するアルミニウム合金を常法に従って溶製し、連続鋳造法、半連続鋳造法(DC鋳造法)等の通常の鋳造法を適宜選択して鋳造する。 <Method for producing aluminum alloy foil>
In the present invention, an aluminum alloy ingot having the above alloy composition is produced by the following steps.
An aluminum alloy having the above composition is melted in accordance with a conventional method, and a normal casting method such as a continuous casting method or a semi-continuous casting method (DC casting method) is appropriately selected and cast.
T>500 (1)
500≧T≧400 かつ t≧0.0004T2-0.4T+101 (2)
(Tは、加熱温度(℃)であり、tは、保持時間(時間)である。) The cast aluminum alloy ingot is warm-rolled at a starting temperature of 150 to 390 ° C. without performing heat treatment under conditions satisfying the following formula (1) or (2).
T> 500 (1)
500 ≧ T ≧ 400 and t ≧ 0.0004T 2 −0.4T + 101 (2)
(T is the heating temperature (° C.), and t is the holding time (hours).)
(1) 熱処理:1ステップ工程例 [ 加熱 ]⇒ 温間圧延
(2) 熱処理:2ステップ工程例 [ 加熱 → 冷却 ]⇒ 温間圧延
(3) 熱処理:2ステップ工程例 [ 加熱 → より高温まで(再)加熱 ]⇒ 温間圧延
(4) 熱処理:3ステップ工程例 [ 加熱 → 冷却 → (再)加熱 ]⇒ 温間圧延 During the period from casting to the start of the warm rolling, a heat treatment is required for causing the aluminum alloy ingot to reach a predetermined warm rolling start temperature. As an example of this heat treatment, as shown in the following (1) to (4), a process including one or more steps combining heating, cooling by forced cooling represented by fan air cooling and water cooling or natural cooling is considered. It is done.
(1) Heat treatment: 1-step process example [Heating] ⇒ Warm rolling
(2) Heat treatment: 2-step process example [heating → cooling] ⇒ Warm rolling (3) Heat treatment: 2-step process example [Heating → higher temperature (re) heating] ⇒ Warm rolling (4) Heat treatment: 3-step process Example [Heating → Cooling → (Re) heating] ⇒ Warm rolling
圧延方向に切り出したアルミニウム合金箔の引張強さおよび0.2%耐力を、島津製作所製インストロン型引張試験機AG-10kNXを使用して測定した。測定条件は、試験片サイズを10mm×100mm、チャック間距離50mm、クロスヘッド速度10mm/分とした。また、乾燥工程を想定し、180℃で1時間の熱処理を行った後のアルミニウム合金箔についても、圧延方向に切り出し、上記と同じく引張強さおよび0.2%耐力を測定した。 <Tensile strength and 0.2% yield strength>
The tensile strength and 0.2% proof stress of the aluminum alloy foil cut in the rolling direction were measured using an Instron type tensile tester AG-10kNX manufactured by Shimadzu Corporation. The measurement conditions were a test piece size of 10 mm × 100 mm, a distance between chucks of 50 mm, and a crosshead speed of 10 mm / min. In addition, assuming the drying step, the aluminum alloy foil after heat treatment at 180 ° C. for 1 hour was cut in the rolling direction, and the tensile strength and 0.2% proof stress were measured in the same manner as described above.
導電率は、四端子法にて電気比抵抗値を測定し、導電率に換算して求めた。 <Conductivity>
The electrical conductivity was determined by measuring the electrical resistivity value by the four probe method and converting it to electrical conductivity.
12μmまで箔圧延されたアルミニウム合金箔を、巾0.6mで長さ6000mのコイル状とし、表面検査機にてピンホールの個数を測定した。測定されたピンホール数を全表面積で除すことで、単位面積1m2当たりのピンホール数を算出し、ピンホール密度とした。 <Pinhole density>
The aluminum alloy foil rolled to 12 μm was coiled with a width of 0.6 m and a length of 6000 m, and the number of pinholes was measured with a surface inspection machine. By dividing the measured number of pinholes by the total surface area, the number of pinholes per 1 m 2 of unit area was calculated and used as the pinhole density.
活物質塗布工程において、正極材試料に切れが発生したか否かを目視で判定した。 <Presence / absence of cutting in the active material application process>
In the active material application step, it was visually determined whether or not the positive electrode material sample was cut.
正極材試料にて活物質の剥離が発生しているか否かを目視で判定した。なお、一部分でも剥離が発生している場合は剥離ありとした。 <Existence of active material peeling>
It was visually determined whether or not the active material was peeled off from the positive electrode material sample. In addition, when peeling had generate | occur | produced in part, it was set as peeling.
本発明の条件範囲内にて製造した実施例1~38では、導電率が高いことに加え、素板強度および乾燥工程を想定した熱処理後の強度が高いため、活物質塗布工程における切れ発生や活物質剥離もなかった。 <Discussion>
In Examples 1 to 38 manufactured within the condition range of the present invention, in addition to high conductivity, the strength of the base plate and the strength after the heat treatment assuming the drying process are high. There was no active material peeling.
温間圧延終了温度が本発明で規定する温度範囲の上限をはずれた比較例52では、素板強度及び180℃で1時間の熱処理を行った後の強度が不足し、活物質塗布工程における切れと活物質の剥離が発生した。
中間焼鈍を施した比較例53では、素板強度及び180℃で1時間の熱処理を行った後の強度が不足し、活物質塗布工程における切れと活物質の剥離が発生した。
温間圧延開始温度が本発明で規定する下限をはずれた比較例54では、温間圧延中の1パスの圧下率が低下するため圧延性が劣化した。
Comparative Example 45 in which the warm rolling start temperature deviates from the upper limit specified in the present invention, Comparative Examples 46 to 49 in which the heat treatment conditions deviate from the upper limit defined in the present invention, both the heat treatment temperature and the warm rolling start temperature are in the present invention In Comparative Examples 50 to 51, which deviated from the upper limit specified in (1), the strength of the base plate and the strength after heat treatment at 180 ° C. for 1 hour were insufficient, and the active material coating process was broken and the active material was peeled off.
In Comparative Example 52 in which the end temperature of the warm rolling is outside the upper limit of the temperature range defined in the present invention, the base plate strength and the strength after heat treatment at 180 ° C. for 1 hour are insufficient, and the cutting in the active material coating process is insufficient. And active material peeling occurred.
In Comparative Example 53 in which the intermediate annealing was performed, the base plate strength and the strength after heat treatment at 180 ° C. for 1 hour were insufficient, and breakage and peeling of the active material occurred in the active material coating process.
In Comparative Example 54 in which the warm rolling start temperature deviated from the lower limit specified in the present invention, the rolling performance deteriorated because the rolling reduction of one pass during the warm rolling decreased.
Claims (2)
- Fe:0.1~0.5mass%(以下mass%を単に%と記す。)、Si:0.01~0.3%、Cu:0.01~0.2%、Mn:0.01%以下を含有し、残部Alと不可避的不純物からなり、引張強さが230MPa以上、0.2%耐力が190MPa以上、導電率が55%IACS以上であり、180℃で1時間の熱処理を行った場合の熱処理後の引張強さが160MPa以上、0.2%耐力が140MPa以上であることを特徴とする電極集電体用アルミニウム合金箔。 Fe: 0.1 to 0.5 mass% (hereinafter mass% is simply referred to as%), Si: 0.01 to 0.3%, Cu: 0.01 to 0.2%, Mn: 0.01% Containing the balance Al and inevitable impurities, the tensile strength is 230 MPa or more, the 0.2% proof stress is 190 MPa or more, the conductivity is 55% IACS or more, and the heat treatment is performed at 180 ° C. for 1 hour. The aluminum alloy foil for electrode current collector characterized by having a tensile strength after heat treatment of 160 MPa or more and a 0.2% proof stress of 140 MPa or more.
- 請求項1に記載の電極集電体用アルミニウム合金箔の製造方法であって、Fe:0.1~0.5%、Si:0.01~0.3%、Cu:0.01~0.2%、Mn:0.01%以下を含有し、残部Alと不可避的不純物からなるアルミニウム合金鋳塊に対し、以下の式(1)又は(2)を満足する条件での熱処理を行うことなく、開始温度150~390℃且つ終了温度150~300℃で温間圧延し、かつ、中間焼鈍を施すことなく冷間圧延と箔圧延を順に実施することを特徴とする電極集電体用アルミニウム合金箔の製造方法。
T>500 (1)
500≧T≧400 かつ t≧0.0004T2-0.4T+101 (2)
(Tは、加熱温度(℃)であり、tは、保持時間(時間)である。)
The method for producing an aluminum alloy foil for an electrode current collector according to claim 1, wherein Fe: 0.1 to 0.5%, Si: 0.01 to 0.3%, Cu: 0.01 to 0 .2%, Mn: 0.01% or less, and heat treatment under conditions satisfying the following formula (1) or (2) for the aluminum alloy ingot composed of the balance Al and inevitable impurities The aluminum for an electrode current collector is characterized in that it is warm-rolled at a start temperature of 150 to 390 ° C. and an end temperature of 150 to 300 ° C., and cold rolling and foil rolling are sequentially performed without intermediate annealing. Manufacturing method of alloy foil.
T> 500 (1)
500 ≧ T ≧ 400 and t ≧ 0.0004T 2 −0.4T + 101 (2)
(T is the heating temperature (° C.), and t is the holding time (hours).)
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WO2014069119A1 (en) * | 2012-10-30 | 2014-05-08 | 住友軽金属工業株式会社 | Aluminium alloy foil |
JP2014109057A (en) * | 2012-12-03 | 2014-06-12 | Uacj Corp | Aluminum alloy foil |
WO2017002420A1 (en) * | 2015-06-30 | 2017-01-05 | 住友電気工業株式会社 | Lead conductor and power storage device |
CN111601905A (en) * | 2017-11-21 | 2020-08-28 | 海德鲁铝业钢材有限公司 | High-strength battery electrode foil for manufacturing lithium ion secondary battery |
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CN105018799A (en) * | 2015-07-15 | 2015-11-04 | 浙江中金铝业有限公司 | Aluminum foil for lithium battery |
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