JP5591583B2 - Aluminum alloy foil for lithium-ion battery electrode current collector - Google Patents

Description

  The present invention relates to an aluminum alloy foil having high strength and excellent workability, which is suitable for a lithium ion battery electrode current collector used for a mobile phone, a notebook personal computer or the like.

  A lithium ion secondary battery is composed of an electrode plate group in which a positive electrode and a negative electrode are wound through a separator, and is manufactured by inserting the electrode plate group into a battery case. The battery case has a cylindrical shape and a rectangular shape. An electrode plate group is prepared according to the shape of the case, and after inserting the electrode plate group, a nonaqueous electrolyte is injected and sealed.

  As the positive electrode active material, lithium cobaltate, a lithium nickel composite compound or the like is used, and as the negative electrode active material, a carbon material capable of adsorbing and desorbing lithium ions such as coke and graphite is used. These positive electrode active materials or negative electrode active materials are stirred and mixed with a binder using polyvinylidene fluoride, etc., applied to the aluminum foil of the positive electrode or the copper foil of the negative electrode, dried, rolled after drying, and rolled or rolled. Heat treatment is performed before and after to improve the adsorptive power, cut into a predetermined size and formed into a sheet shape, and used as an electrode of a lithium ion secondary battery.

  Although the aluminum foil is used for the positive electrode current collector, the expansion of the negative electrode active material can be achieved by using an aluminum foil having an elongation to break of 3% or more after being charged once or more. It has been proposed to improve cycle characteristics by preventing the positive electrode from deteriorating and breaking during charge and discharge cycles by repeated shrinkage.

JP 2007-234277 A JP 2006-134762 A

  As described above, the aluminum foil for the positive electrode current collector needs to have a large elongation in order to improve cycle characteristics. However, when recrystallization is performed by heat treatment, the temperature exceeds 200 ° C. When heated, the active material changes in quality and predetermined electrical characteristics cannot be obtained. Accordingly, there is a demand for an aluminum foil for a positive electrode current collector that is recrystallized at a temperature as low as 200 ° C. or less to increase elongation.

  On the other hand, it is necessary to maintain sufficient strength in the next active material rolling process without softening with respect to heating in the drying process after application of the active material. There is a demand for an aluminum foil for a positive electrode current collector.

  The present invention solves the above-mentioned conventional problems, and does not soften at a temperature of about 100 ° C., starts to soften at about 120 ° C., and further recrystallizes at a temperature as low as 200 ° C. or less to increase elongation. In order to obtain an aluminum foil, the composition of the aluminum foil, the structural properties, the strength characteristics, etc. were studied, and the purpose was to have sufficient strength during the application and rolling of the active material during electrode production. And to provide an aluminum alloy foil for a lithium ion battery electrode current collector that can be softened at a subsequent temperature rise of about 120 ° C. or higher and recrystallized at a temperature as low as 200 ° C. or lower to ensure large elongation. is there.

In order to achieve the above object, the aluminum alloy foil for a lithium ion battery electrode current collector according to claim 1 is in mass%, Fe: 0.8% or more, 2.0% or less, Si: 0.35% or less, Ti : 0.05% or less, consisting of the balance Al and unavoidable impurities, no occurrence of pinholes, and 800 or more Al-Fe compounds having an equivalent circle diameter of 10 to 50 nm per cubic μm, The tensile strength is 160 MPa or more, the tensile strength after oil bath heat treatment at 100 ° C. for 1 minute is 150 MPa or more, and the tensile strength after oil bath heat treatment at 120 ° C. for 1 minute is less than 150 MPa. And Hereinafter, all alloy component values are indicated by mass%.

  An aluminum alloy foil for a lithium ion battery electrode current collector according to claim 2 is characterized in that, in claim 1, it further contains Mn: 0.05% or less and Cu: 0.05% or less.

  According to the present invention, it has sufficient strength at the time of application, drying, and rolling during electrode production, and then begins to soften at a low temperature of about 120 ° C., and further undergoes heat treatment at a temperature as low as 200 ° C. or less, resulting in large elongation. When the positive electrode and the negative electrode are wound through a separator and further incorporated into a battery as an electrode, it has sufficient ductility and is not easily broken, and even when the battery is repeatedly charged and discharged, the electrode expands and contracts. Thus, there is provided an aluminum alloy foil for a lithium ion battery electrode current collector, which can prevent electrode deterioration and breakage due to, and can ensure a sufficient cycle life.

The significance and reasons for limitation of the components of the aluminum alloy foil for a lithium ion current collector according to the present invention will be described.
Fe:
It is an important alloying element that determines the characteristics of the aluminum alloy foil for the lithium ion current collector of the present invention, which improves strength, prevents softening when heated to about 100 ° C, and starts softening at a temperature of about 120 ° C. It further functions to lower the recrystallization temperature. These functions can be obtained by controlling both the solid solution amount of Fe and the precipitation state to improve the strength and lower the recrystallization temperature.

  Fe dissolved in the aluminum alloy foil is finely precipitated as an Al—Fe-based compound having a particle size of less than 5 nm when heated at about 100 ° C., thereby suppressing dislocation movement and softening of the material. On the other hand, at a temperature of about 120 ° C. or higher, the diffusion rate of the dissolved Fe is slow, so that the recovery rate of the processed structure is faster than the precipitation of the Al—Fe-based compound, and softening starts. Therefore, by dispersing a large number of Al-Fe fine compounds having a particle size of 10 to 50 nm that are not compatible with the Al substrate (matrix), the processed structure is easily recovered during heat treatment, and the recrystallization temperature is lowered. Even with heat treatment at 200 ° C. or less, large elongation can be obtained.

  The preferable content of Fe is in the range of 0.8% or more and 2.0% or less, and if it is less than 0.8%, a tensile strength of 160 MPa or more cannot be obtained even if the final cold rolling rate is 80% or more, In addition, the amount of Fe dissolved is reduced, the strength is lowered by heating at about 100 ° C., and the recrystallization temperature cannot be lowered to 200 ° C. or lower. If it exceeds 2.0%, a coarse Al—Fe compound exceeding several hundred μm is formed at the time of casting, which causes pinholes (holes) generation during foil rolling, and it is difficult to produce a sound foil material. Become. A more preferable content range of Fe is 1.2 to 1.7%.

Si:
Although it contains as an impurity, it is preferable to regulate to 0.35% or less. When the Si content exceeds 0.35%, precipitation of Si alone or an Al—Fe—Si based compound is accelerated at around 170 ° C., and ductility is lowered. More preferably, the content is restricted to 0.1% or less.

Ti:
It has the effect of making the ingot structure fine, and helps to reduce fluctuations in mechanical properties on a mass production scale. The preferable Ti content is in the range of 0.05% or less, and if it exceeds 0.05%, it may cause pinholes during foil rolling. B can be added together with Ti to obtain the same effect, but the content of B in the aluminum alloy foil is preferably 0.01% or less for the same reason.

Mn:
Mn functions to improve strength. The preferable content of Mn is in the range of 0.05% or less, and when it exceeds 0.05%, a coarse Al—Mn compound is easily formed, and the generation of pinholes is induced. A more preferable content range of Mn is 0.02% or less.

Cu:
Functions to improve strength. The preferable content of Cu is in the range of 0.05% or less. When the content is large, the amount of dissolved Cu increases and the movement of dislocations is suppressed. As a result, recrystallization is not completed at 200 ° C. or less, which is large. Elongation cannot be obtained.

  The aluminum alloy foil contains inevitable impurities such as Mg, Zn, Ga, Ni, Cr, Sn, Pb, and V. The contents of Zn, Ga, Ni, Cr, Sn, Pb and V are preferably regulated to 0.02% or less in order not to raise the recrystallization temperature. As for Mg, as the content increases, Mg concentrates at the interface between the aluminum base and the aluminum oxide film to form an MgO layer. This MgO layer becomes a weak boundary layer and decreases the adhesiveness. It is preferable to regulate to% or less.

Dispersion state of Al-Fe compound:
When hot rolling or cold rolling is performed in a state containing Fe of 0.8% or more, the Al—Fe compound having a particle size of about 50 to 100 μm formed at the time of casting is divided, and a foil material having a thickness of 50 μm or less Then, the fine particles having a particle size of 50 nm or less are dispersed. These fine compounds increase the strength during cold rolling. In addition, these Al—Fe compounds are not compatible with the Al substrate, and when the temperature rises, the interface between the Al—Fe compound and the Al substrate becomes a source of vacancies, facilitating the movement of dislocations. It has been found that there is an effect of lowering the crystallization temperature. In addition, all the particle diameters of a compound are shown by a circle equivalent diameter.

  As a result of investigating the correlation between the dispersion state of the Al—Fe compound and the recrystallization temperature in detail, when 800 or more fine Al—Fe compounds having a particle size of 10 to 50 nm are present per cubic μm, the recrystallization is performed at 200 ° C. or less. Crystals were found to be complete. The abundance of the compound was quantified using a transmission electron microscope (transmission electron microscopy, translated by Shotaro Moromi, Corona, page 568). The number of compounds was measured from the bright field image, and the number of compounds per unit volume was calculated from the area of the measurement area and the sample thickness at the measurement position. The thickness of the sample was calculated from the product of the number of black and white stripes observed and the extinction distance using extinction stripes observed with a transmission electron microscope.

  If the metal structure recovers at a temperature of 120 ° C. and recrystallization is started, a large elongation can be obtained by a heat treatment at 200 ° C. or less. For this purpose, it is necessary that the tensile strength after oil bath heat treatment at 120 ° C. for 1 minute is less than 150 MPa. When the strength reduction after oil bath heat treatment at 120 ° C. for 1 minute is small and the tensile strength becomes 150 MPa or more, the degree of recovery is delayed and large elongation cannot be obtained by heat treatment at 200 ° C. or less. In order to obtain a large elongation, a heat treatment exceeding 200 ° C. is required, resulting in a decrease in performance of the active material.

Manufacturing process:
The aluminum alloy foil for a lithium ion battery electrode current collector of the present invention is obtained by melting and casting an aluminum alloy having the above composition, and homogenizing the obtained ingot, hot rolling, cold rolling, intermediate annealing, final Manufactured through cold rolling. The homogenization treatment is preferably performed at a temperature of 400 to 580 ° C., and if it is less than 400 ° C., the fluctuation of mechanical properties becomes remarkable in a mass production scale foil material, which is not preferable. When the temperature exceeds 580 ° C., a part of the Al—Fe compound is coarsened, and part of the Al—Fe compound is dissolved (so-called Ostwald growth), and the number of dispersed Al—Fe compounds at the foil material stage is reduced. Recrystallization is difficult to complete below ℃. The holding time is preferably 24 hours or less from the viewpoint of manufacturing cost.

  Hot rolling is performed so that the coiling temperature is lower than the recrystallization temperature, preferably 260 ° C. or lower. This is to suppress the decrease in the amount of solid solution Fe and to leave the dislocations introduced in the hot rolling process to increase the number of precipitation sites, thereby promoting fine precipitation during intermediate annealing. The wound hot-rolled sheet is subjected to cold rolling and further intermediate annealing, with or without intermediate annealing.

  The intermediate annealing after the cold rolling is performed at a temperature of 300 to 340 ° C. for 12 hours or less. This intermediate heat treatment is performed to reduce fluctuations in the mechanical properties of the material to be manufactured on a mass production scale. The effect is small at less than 300 ° C, and the recrystallized grains become coarse when the temperature exceeds 340 ° C. Sometimes causes pinholes. The holding time is preferably 12 hours or less from the viewpoint of manufacturing cost. More preferably, it is 2 h or more and 8 h or less.

  The rolling ratio in the final cold rolling after the intermediate annealing is closely related to the recrystallization behavior and requires strict control. The rolling rate of final cold rolling is preferably 85% or more, and more preferably 95% or more. When the rolling ratio of the final cold rolling is less than 85%, recrystallization hardly occurs, and even if heat treatment is performed at a temperature of 200 ° C. or less, recrystallization is not completed and large elongation cannot be obtained. In each cold rolling, if the material temperature becomes high, the work structure is recovered and the driving force for recrystallization is reduced. Therefore, even if the final product foil is heat-treated at a temperature of 200 ° C. or less, the recrystallization is not completed. , You can not get a large elongation. Accordingly, the winding temperature in each cold rolling in the final cold rolling is preferably less than 90 ° C.

  Examples of the present invention will be described below in comparison with comparative examples to demonstrate the effects. In addition, these Examples show one embodiment of this invention, and this invention is not limited to these.

Example 1 and Comparative Example 1
An aluminum alloy having the composition shown in Table 1 was melted and ingot-formed by a semi-continuous casting method, and the resulting ingot was homogenized at 520 ° C. for 10 hours. Subsequently, hot rolling was performed in a temperature range of 450 to 230 ° C. and winding was performed at 230 ° C. to obtain a hot rolled plate having a thickness of 3 mm. Further, the obtained hot rolled sheet was subjected to intermediate annealing for 4 hours at a temperature of 330 ° C.

  Thereafter, cold rolling was performed at a winding temperature of 90 to 120 ° C. to a thickness of 0.5 mm, and then an intermediate annealing was performed at a temperature of 310 ° C. for 6 hours. Next, as the final cold rolling, cold rolling was repeated at a winding temperature of 60 to 80 ° C. to obtain an aluminum alloy foil having a thickness of 15 μm. In each cold rolling after the intermediate annealing, by adjusting the reduction amount, adjusting the coil temperature after each cold rolling sufficiently to perform the next rolling, etc., the winding temperature is It was made to become temperature.

  Using the obtained aluminum alloy foil as a test material, the presence or absence of pinholes was observed and the tensile strength was measured. In addition, the number of Al—Fe compounds having a particle diameter of 10 to 50 nm per cubic μm was measured by the transmission electron microscopy. Furthermore, the tensile strength after an oil bath heat treatment at 100 ° C. for 1 minute was measured, and the test material after the heat treatment was further subjected to an oil bath heat treatment at 170 ° C. for 1 minute to measure the tensile strength and elongation. Separately from the above, the test material after oil bath heat treatment at 100 ° C. for 1 minute was subjected to oil bath heat treatment at 120 ° C. for 1 minute, and the tensile strength was measured. These results are shown in Table 2. In Tables 1 and 2, those outside the conditions of the present invention are underlined.

  As shown in Table 2, all of the test materials 1 to 6 according to the present invention have no pinholes, and the test material (aluminum alloy foil having a thickness of 15 μm) has an Al—Fe-based compound with a particle size of 10 to 50 nm. 800 pieces / cubic μm or more, tensile strength is 160 MPa or more, tensile strength after heat treatment at 100 ° C. is 150 MPa or more, tensile strength after heat treatment at 120 ° C. is less than 150 MPa, and elongation after heat treatment at 170 ° C. is 4 % Or more.

  On the other hand, since the test material 7 has an Fe content of less than 0.8%, the strength decreases after treatment at 100 ° C. and becomes lower than 150 MPa, and the number of Al—Fe compounds having a particle size of 10 to 50 nm is 800 / cubic. Less than μm, the elongation after heat treatment at 170 ° C. was less than 3%. Since the test material 8 had an Fe content exceeding 2%, a coarse compound was formed during casting, and pinholes were generated during foil rolling. Since the test material 9 contains Si exceeding 0.35%, precipitation of the Al—Fe—Si compound was promoted by heat treatment at 170 ° C., and the elongation was less than 3%.

  Since the test material 10 contained more than 0.05% Ti, a coarse intermetallic compound was formed, and pinholes were generated during foil rolling. Since the test material 11 has an Fe content of less than 0.8%, the strength decreases after treatment at 100 ° C. and becomes lower than 150 MPa. In addition, the number of Al—Fe compounds having a particle diameter of 10 to 50 nm was less than 800 / cubic μm, and the elongation after heat treatment at 170 ° C. was less than 3%. The test material 12 has the characteristics of the conventional material 1085 alloy. The Al-Fe compound having a particle size of 10 to 50 nm was less than 800 / cubic μm, and the elongation after heat treatment at 170 ° C. was less than 3%.

Example 2 and Comparative Example 2
Using the ingot of alloy B in Table 1, an aluminum alloy foil having a thickness of 15 μm was produced under the production conditions shown in Table 3, and the obtained aluminum alloy foil was used as a test material in the same manner as in Example 1. The presence or absence of holes was observed, the tensile strength was measured, and the number of Al—Fe compounds having a particle size of 10 to 50 nm per cubic μm was measured by the transmission electron microscopy. Furthermore, the tensile strength after an oil bath heat treatment at 100 ° C. for 1 minute was measured, and the test material after the heat treatment was further subjected to an oil bath heat treatment at 170 ° C. for 1 minute to measure the tensile strength and elongation. Separately from the above, the test material after oil bath heat treatment at 100 ° C. for 1 minute was subjected to oil bath heat treatment at 120 ° C. for 1 minute, and the tensile strength was measured. These results are shown in Table 3. In Table 3, those outside the conditions of the present invention are underlined.

  As shown in Table 3, none of the test materials 13 to 15 according to the present invention had pinholes during foil rolling, and the test material (aluminum alloy foil having a thickness of 15 μm) had an Al particle size of 10 to 50 nm. -Fe compounds are present in 800 pieces / cubic μm or more, tensile strength is 160 MPa or more, tensile strength after heat treatment at 100 ° C. is 150 MPa or more, tensile strength after heat treatment at 120 ° C. is less than 150 MPa, after heat treatment at 170 ° C. The elongation of 4% or more.

  On the other hand, since the test material 16 has a homogenization treatment temperature exceeding 580 ° C., the Ostwald growth of the Al—Fe based compound is promoted, and as a result, the Al—Fe based compound having a particle size of 10 to 50 nm becomes 800 nm. The number was less than 1 piece / cubic μm, and the elongation after heat treatment at 170 ° C. was less than 3%. Since the test material 17 was maintained at a temperature higher than 340 ° C. for a long time, the crystal grains were coarsened, and pinholes were generated during foil rolling.

  Since the test material 18 had a final cold rolling reduction rate of less than 85%, recrystallization during 170 ° C. heat treatment was delayed, and the elongation was less than 3%. Since the test material 19 had a hot rolling coiling temperature of 340 ° C., which is equal to or higher than the recrystallization temperature, the number of Al—Fe compounds having a particle size of 10 to 50 nm was less than 800 / cubic μm, and the elongation after 170 ° C. heat treatment was increased. Less than 3%. Since the test material 20 had a final cold rolling coiling temperature of 140 ° C., the recovery of the processed structure was promoted, the tensile strength after 120 ° C. heat treatment was 150 MPa or more, and recrystallization during 170 ° C. heat treatment was delayed, The elongation was less than 3%.

Claims (2)

In mass%, Fe: 0.8% or more and 2.0% or less, Si: 0.35% or less, Ti: 0.05% or less, consisting of the balance Al and inevitable impurities , generation of pinholes There are not less than 800 Al-Fe compounds having an equivalent circle diameter of 10 to 50 nm per cubic μm, the tensile strength is 160 MPa or more, and the tensile strength after oil bath heat treatment at 100 ° C. for 1 minute is 150 MPa. The aluminum alloy foil for a lithium ion battery electrode current collector, further having a tensile strength after oil bath heat treatment at 120 ° C. for 1 minute of less than 150 MPa. The aluminum alloy foil for a lithium ion battery electrode current collector according to claim 1, further comprising, by mass%, Mn: 0.05% or less and Cu: 0.05% or less.