Patent Application
20130224582
1. Field of the Invention
The present invention relates to a novel metal foil for a negative electrode collector. More specifically, the present invention relates to a metal foil for a negative electrode collector that is used as a collector in a lithium ion battery, a lithium ion capacitor, an electrical double layer capacitor and the like.
2. Description of the Related Art
In lithium ion batteries, lithium ion capacitors and electrical double layer capacitors and the like, positive electrode collectors are made from aluminum, stainless steel and the like, and negative electrode collectors are made from stainless steel, copper, nickel and the like.
Higher voltages are required in order to improve the energy density in these lithium ion batteries, lithium ion capacitors, electrical double layer capacitors and the like. In order to increase the energy density, it is preferable to use a pre-doping technique and reduce the negative electrode potential. In addition, in order to carry out pre-doping with good efficiency, it is necessary to provide through holes in a collector. That is, it is possible to support lithium ions in a negative electrode active substance by providing through holes in a collector so as to enable reversible transfer of the lithium ions.
Punching, mesh processing, expansion processing, net processing and the like are known as methods for preparing collectors having through holes, but through holes formed using these methods are generally 0.1 to 0.3 mm in size (see Japanese Patent Application Publication No. 2004-103314). However, simply providing through holes reduces the strength of a collector, and through holes having relatively large diameters, such as those mentioned above, exacerbate the problem of reduced strength.
In contrast, proposals have been made for electrodes using collectors having relatively fine through holes. For example, a lithium ion capacitor which is provided with a positive electrode comprising a substance able to reversibly support lithium ions and/or anions and a negative electrode comprising a substance able to reversibly support lithium ions and which is provided with an aprotic organic solvent electrolyte solution of lithium salt as an electrolyte, wherein the capacitor has a collector comprising a metal foil in which (1) the negative electrode and/or positive electrode are doped with lithium ions by electrochemically connecting the negative electrode and/or the positive electrode with a lithium ion supply source, (2) the potential of the positive electrode is 2.0 V or lower after short circuiting the positive electrode and the negative electrode, and (3) the aforementioned positive electrode and/or negative electrode have a multiplicity of through holes between the front and rear surfaces and the average inscribed circle diameter of these through holes is 100 μm or smaller, is known (see WO 2008/078777).
In addition, a collector comprising an aluminum etched foil which has a thickness of 20 to 45 μm, an apparent density of 2.00 to 2.54 g/cm3 and an air permeability of 20 to 120 s and which has a multiplicity of through holes between the front and rear surfaces, wherein 80% or more of the aforementioned through holes have hole diameters of 1 to 30 μm, is known as a positive electrode collector used in a lithium ion capacitor such as that mentioned above (see Japanese Patent Application Publication No. 2009-62595).
However, electrodes that use conventional negative electrode collectors have relatively high resistance (internal resistance) for electrodes, which can lead to concerns regarding adverse effects on charging and discharging characteristics when used in batteries and the like. Causes of increased electrode resistance include the state of distribution of through holes in a collector and adhesion between a collector and an active substance, and it is therefore necessary to improve these characteristics.
Therefore, the main objective of the present invention is to provide a metal foil for a negative electrode collector, by which it is possible to achieve a lower resistance value.
As a result of diligent research into the problems inherent in the prior art, the inventors of the present invention found that it was possible to achieve the above-mentioned objective by controlling the distribution of through holes within a specified range, and thereby completed the present invention.
That is, the present invention relates to the following metal foil for a negative electrode collector.
1. A metal foil for a negative electrode collector, which has a plurality of openings that reach a foil rear surface from a foil front surface and which has a region having a through hole density of 1000 holes/cm2 or more.
2. The metal foil for a negative electrode collector according to 1 above, wherein an average internal diameter of the through holes is 100 μm or lower.
3. The metal foil for a negative electrode collector according to in 1 or 2 above, wherein the aperture ratio of the openings is 30% or lower.
4. The metal foil for a negative electrode collector according to any one of 1 to 3 above, wherein 2.0>[the foil thickness (μm)/the aperture ratio (%)]>0.25 is established.
5. The metal foil for a negative electrode collector according to any one of 1 to 4 above, further containing a region having a through hole density of less than 1000 holes/cm.
6. The metal foil for a negative electrode collector according to any one of 1 to 5 above, wherein the area of the region having a through hole density of 1000 holes/cm or more is 100 mm2 or more.
According to the present invention, by controlling the distribution of through holes within a specified range, it is possible to achieve a lower resistance value than conventional collectors when using the collector in an electrode.
This type of metal foil for a negative electrode collector can be preferably used as a collector for a lithium ion battery, a lithium ion capacitor, and electrical double layer capacitor and the like. In particular, the metal foil for a negative electrode collector of the present invention is useful as a negative electrode collector of a lithium ion capacitor or a lithium ion secondary battery which comprises 1) a positive electrode comprising a substance able to reversibly support lithium ions and/or anions, 2) a negative electrode comprising a substance able to reversibly support lithium ions, and 3) an electrolyte solution that contains lithium ions, and in which the positive electrode and/or negative electrode are doped with lithium ions.
a) is a diagram showing an example of a pattern of a through hole region and a support region in a metal foil produced in the examples, and
The metal foil for a negative electrode collector of the present invention (the metal foil of the present invention) is characterized by having a plurality of through holes that reach the foil rear surface from the foil front surface and having a region having a through hole density of 1000 holes/cm2 or more (a through hole region). That is, the metal foil of the present invention is characterized by having a plurality of through holes that reach the foil rear surface from the foil front surface and having a through hole density of 1,000 holes/cm2 or more in a 1 cm2 region at an arbitrary location.
The metal used in the metal foil of the present invention can be a material (a metal foil) according to those used in conventional negative electrode collectors for batteries. For example, it is possible to preferably use copper, stainless steel, nickel, aluminum or an alloy containing at least one of these. Of these, it is preferable to use copper from the perspective of electrochemical characteristics as a negative electrode collector. When using copper, it is possible to use a rolled copper foil, an electrolytic copper foil and the like.
In addition, the thickness of the metal foil is not limited, but is generally within the range 3 to 100 μm, and can be set as appropriate according to, for example, the type of metal foil used. For example, when using a copper foil as the metal foil, a thickness of 8 to 25 μm is more preferred.
In the present invention, the through holes are holes 13 that penetrate from the front surface 11 to the rear surface 12 of the metal foil 10, as shown in
As mentioned above, the through hole density is 1000 holes/cm2 or higher, preferably 1500 to 30000 holes/cm2, and more preferably 2000 to 20000 holes/cm2. By setting the through hole density to fall within the above-mentioned range, the distance between through holes is reduced and ions can pass more easily, which therefore contributes to achieving a lower resistance value.
The size of the through holes is also not limited, but the average internal diameter of the through holes is preferably 100 μm or lower, and especially 90 μm or lower. By setting the average internal diameter to fall within the above-mentioned range, it is possible to more evenly control the thickness of a coating film when an active substance (slurry) is coated on the metal foil of the present invention. In the present invention, the average internal diameter of the through holes means the diameter calculated from the average area of the through holes, on the assumption that the through holes are circles.
The aperture ratio in the metal foil of the present invention is generally 40% or lower, and preferably 30% or lower. In the prior art, the aperture ratio was set to a higher value in order for ions to pass through the collector more easily, but a larger aperture ratio resulted not only in a reduction in foil strength, but also made it difficult to evenly coat an active substance on the foil, resulted in the active substance inside the through holes shrinking during drying after coating, and led to the active substance peeling or cracking more readily. In contrast, by setting the aperture ratio of the metal foil of the present invention to fall within the above-mentioned range, it is possible to maintain a higher foil strength. In the present invention, the aperture ratio is the ratio of the total area occupied by openings of through holes relative to the overall area of the region containing through holes on the surface of the metal foil.
In addition, it is preferable for the foil thickness and aperture ratio of the metal foil of the present invention to satisfy the relationship:
2.0>[the foil thickness(μm)/the aperture ratio(%)]>0.25.
It is particularly preferable for 1.8≧[(the foil thickness (μm)/the aperture ratio (%)]≧0.27. If the above-mentioned value is 0.25 or lower, there are concerns that the strength of the foil will significantly deteriorate. However, if the above-mentioned value is 2.0 or higher, this causes problems such as the pre-doping time increasing.
The metal foil of the present invention may contain a region other than a through hole region. That is, the metal foil of the present invention may contain a region having a through a hole density of less than 1000 holes/cm2 (preferably 500 holes/cm2 or less, more preferably 100 holes/cm2 or less, and most preferably 0 holes/cm2 (hereinafter referred to as a “support region”). If the metal foil of the present invention contains a support region, the support region acts to support the through hole region, and it is therefore possible to effectively maintain the strength of the overall metal foil.
The area and pattern of the support region can be set as appropriate according to, for example, the thickness, material and intended use of the metal foil of the present invention. For example, as shown in
The metal foil of the present invention can be produced using a publicly known method except that the through hole density and the like is controlled within a prescribed range. For example, it is possible to obtain the metal foil of the present invention by etching a metal foil having a prescribed thickness.
As a method for etching, it is possible to preferably use a method that includes, for example, 1) a step of forming a photoresist film on the surface of a metal foil (a photoresist film formation step), 2) a step of exposing the photoresist film to UV light via a photomask (an exposure step), 3) a step of removing a prescribed pattern part from the photoresist film by developing (a developing step), 4) a step of forming through holes in the metal foil by etching (an etching step), and 5) a step of removing the remaining photoresist film (a peeling step).
The above-mentioned method will now be explained with reference to
Firstly, a metal foil in which through holes are to be formed is prepared as shown in “1, Material” in
In addition, it is possible to use not only one type of metal foil or alloy foil, but also a clad foil comprising the same types of metal or alloy. In cases where an aluminum foil or aluminum alloy foil is used as the metal foil, the components of the aluminum or aluminum alloy can be selected as appropriate from among pure aluminum (JIS 1000 type), an aluminum-manganese (Al—Mn)-based alloy (JIS 3000 type), an aluminum-magnesium (Al—Mg)-based alloy (JIS 5000 type), and aluminum-iron (Al—Fe)-based alloy (JIS 8000 type) and the like according to the type of electrolyte in the secondary battery.
Next, a photoresist film is formed on the surface of the metal foil in the photoresist film formation step shown in “2, Resist coating” in
The synthetic resin can be one known as a photoresist film. For example, it is possible to use an acrylic resin, polyethylene terephthalate, polypropylene, polyethylene and the like. In the present invention, an acrylic resin is preferably used. More specifically, it is preferable to use a negative resist formed from an acrylic resin.
The thickness of the photoresist film formed on the metal foil can be set as appropriate according to the type of synthetic resin used, but can generally be 1 to 50 μm.
The photoresist film may be formed on one or both sides of the metal foil. In the present invention, it is particularly preferable to form a photoresist film on both surfaces of the metal foil. That is, if a photoresist film is formed on both surfaces, as shown in
The photoresist film is exposed to UV light via a photomask in the exposure step shown in “3, Exposure” in
The exposure method and photomasking method can be carried out by forming a desired pattern in accordance with conditions set with a publicly known exposure device (a photo-plotter and the like). As shown in “3, Exposure” in
In the developing step shown in “4, Developing” in FIG. 1, a prescribed pattern part of the photoresist film is removed by developing. The developing method can be similar to publicly known methods. Removal of the photoresist film can also be carried out in accordance with known developing methods. For example, by dipping for approximately 1 minute in a 1% aqueous solution of Na2CO3 (sodium carbonate) at a liquid temperature of 30° C., it is possible to remove the photoresist film.
In the etching step shown in “5, Etching” in
The etching conditions can be set according to publicly known etching methods. For example, the liquid temperature can be approximately 25 to 60° C., and the treatment time can be approximately 10 seconds to 5 minutes.
In the peeling step, the remaining photoresist film is removed. The photoresist film can be removed using, for example, a weakly alkaline aqueous solution. The weakly alkaline aqueous solution can be, for example, an aqueous solution of sodium hydroxide. In addition, after removing the photoresist film, a treatment such as drying the metal foil may be carried out if necessary in the present invention.
The metal foil of the present invention, which is obtained as described above, can be formed into a product by winding into a coil if necessary. Thereafter, the metal foil of the present invention may be cut to an appropriate size if necessary and supplied to a step in which an active substance is coated on the metal foil.
The features of the present invention will now be explained in greater detail, through the use of examples and comparative examples. However, the scope of the present invention is not limited to the working examples.
Moreover, the methods for measuring various physical properties were carried out as follows.
The surface was observed under a microscope (manufactured by Keyence Corporation), and the through hole density was measured.
An image obtained from the above-mentioned microscope (10 or more through holes were included in the field of view. If or more holes were not included, the magnification ratio was altered so that 10 or more through holes were included in the field of view) was binarized using image processing software provided with the microscope, and the areal ratio of the through hole parts was measured and deemed to be the aperture ratio.
Photographs of 10 fields of view were taken at random using the same method as that used in (2) above, image analysis was carried out in order to measure the number of through holes and the total through hole area, and the internal diameters of the through holes were calculated on the assumption that all the through holes were identical circles. The image analysis device was a “PCA11” multi-purpose high-speed image analysis device (manufactured by System Science Co., Ltd.).
As a metal foil, a coiled electrolytic copper foil having a thickness of 10 μm, a width of 300 mm and a length of 250 m was dip coated with a solution of an acrylic resin negative photoresist so as to coat both surfaces of the copper foil with the acrylic resin at a thickness of 5 μm, and the coated copper foil was then dried at 80° C. One surface of the metal foil was irradiated with UV light at an intensity of 100 mj/cm2 via a photomask on which the pattern shown in
A metal foil was obtained in the same way as Example 1, except that the pattern shown in
The through hole density and the like of the metal foils for negative electrode collectors obtained in Example 1 and Comparative Example 1 were investigated. These results are shown in Table 1.
In use of the metal foils for negative electrode collectors obtained in Example 1 and Comparative Example 1, negative electrodes were prepared by cutting out the obtained metal foils, which have lengths of approximately 50 cm, at apart approximately m and a part approximately 900 m in the length direction after the start of the etching, than coating with a slurry containing an active substance composed of carbon particles, and then cutting to sizes of 10 cm×20 cm. Here, the coating characteristics in the above-mentioned slurry-coating step were confirmed. Next, a battery such as that shown in
Moreover, the physical properties shown in Table 2 were measured as follows.
(1) Capacity (mAh)
The above-mentioned cell was subjected to a charging and discharging test and the capacity was calculated from the discharging time. The discharging was carried out at a current of 53 mA/cm2, and the capacity was calculated by multiplying the current by the discharging time required for the voltage to reach 2.2 V from 3.8 V.
(2) Internal Resistance (mΩ)
In the above-mentioned test, the internal resistance was calculated using Ohm's Law from the value of the discharging current and the value of the voltage drop that occurred when switching between charging and discharging (the IR drop).
An electrode coating liquid containing a negative electrode active substance was coated (to a thickness of 20 μm on each surface) on both surfaces of a copper collector having through holes using a die coater. A leak check (10 m) and a check for the occurrence of surface patterns (the occurrence of differences in coating thickness) were carried out as checks following coating. A case in which a leak or a surface pattern was confirmed visually was evaluated as “X” and a case in which these were not confirmed was evaluated as “◯”.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010-084114 | Mar 2010 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2011/055035 | 3/4/2011 | WO | 00 | 12/12/2012 |
