JP2009266699A - Electrode foil for battery, positive electrode plate, battery, vehicle, battery-mounting equipment, manufacturing method of electrode foil for battery, and manufacturing method of positive electrode plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode foil for a battery which is used for a positive electrode plate of the battery and having superior corrosion resistance and conductivity though with reduced, to provide the positive electrode plate using this positive electrode foil, to provide the battery using this positive electrode foil, and furthermore, to provide a vehicle using this battery, to provide battery-mounting equipment, to provide a manufacturing method of the electrode foil for the battery, and to provide a manufacturing method of the positive electrode foil. <P>SOLUTION: The electrode foil 32 for the battery includes an aluminum electrode foil 33, and corrosion resistance layers 34A, 34B of thickness 5 to 100 nm, which is formed on surfaces 33a, 33b of the aluminum electrode foil, and composed of metal zirconium which is formed by directly coming into contact with metal aluminum to form the aluminum electrode foil. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a battery electrode foil, a positive electrode plate, a battery, a vehicle using the same, a battery-mounted device, a method for manufacturing a battery electrode foil, and a method for manufacturing a positive electrode plate.

In recent years, with the spread of portable electronic devices such as mobile phones, notebook computers, and video camcorders and vehicles such as hybrid electric vehicles, the demand for batteries used for these driving power sources is increasing.
Among such batteries, there is a battery using a positive electrode foil based on an aluminum electrode foil. For example, the lithium ion battery using the positive electrode plate which apply | coated the positive electrode active material containing Li compound to such aluminum electrode foil is mentioned.

However, an aluminum oxide layer (alumina layer) is formed on the surface of the aluminum electrode foil, and even if a positive electrode active material is formed on such an aluminum electrode foil, the conductivity between them is low. On the other hand, this aluminum oxide layer is not sufficiently resistant to corrosion, and corrosion may occur in the applied positive electrode active material paste or the electrolyte in the battery.
Therefore, in Patent Document 1, a carbon film is formed on the surface of an aluminum electrode foil (aluminum current collector) in order to improve corrosion resistance and conductivity. In Patent Document 2, the surface of the current collector is formed. A method for forming a conductive coating layer made of carbon, platinum, or gold after etching is disclosed.

Japanese Patent Laid-Open No. 10-106585 Japanese Patent Laid-Open No. 11-250900

However, as in Patent Documents 1 and 2, when forming a carbon film by sputtering with high mass productivity, an insulating diamond-like carbon (DLC) film is formed, which is rather conductive. May decrease.
On the other hand, using platinum or gold is expensive and not practical.

  The present invention has been made in view of such problems, and an object thereof is to provide a battery electrode foil used for a positive electrode plate of a battery, which is inexpensive but has good corrosion resistance and conductivity. To do. Furthermore, a positive electrode plate using the battery electrode foil, a battery using the positive electrode foil, a vehicle using the positive electrode foil, a battery-equipped device, and a method for manufacturing the battery electrode foil are provided. And it aims at providing the manufacturing method of a positive electrode plate.

  The solution includes: an aluminum electrode foil; and a corrosion-resistant layer having a thickness of 5 to 100 nm made of metal zirconium formed on the surface of the aluminum electrode foil and made in direct contact with the metal aluminum forming the aluminum electrode foil. It is the electrode foil for batteries provided.

The battery electrode foil of the present invention includes a corrosion-resistant layer made of zirconium. Zirconium is a valve metal and forms an oxide layer (zirconia layer) on its surface to prevent the progress of internal corrosion. Even if it is in a state of being easily oxidized due to a potential, it is a battery electrode foil with good corrosion resistance that is not easily corroded.
Furthermore, this corrosion-resistant layer (zirconium and its surface oxide layer) has conductivity, for example, Au (2.35 μΩ · cm), Cu (1), such as Zr (conductivity 40 μΩ · cm). Although not as high as .67 μΩ · cm), it has better or comparable conductivity than Ti (42 μΩ · cm). Note that Al ₂ O ₃ (10 ²⁰ μΩ · cm). In addition, this corrosion-resistant layer is in direct contact with the metallic aluminum forming the aluminum electrode foil.

Therefore, in the battery electrode foil of the present invention, since the aluminum oxide layer (alumina layer) formed on the surface of the normal aluminum electrode foil is not interposed between the aluminum electrode foil and the corrosion resistant layer, the contact resistance is low. A battery electrode foil is obtained.
Furthermore, when a corrosion-resistant layer made of zirconium was formed on the surface of the aluminum electrode foil, the corrosion resistance was investigated (corrosion gas amount investigation), and it was found that the underlying aluminum electrode foil might corrode at 5 nm or less. On the other hand, when the thickness exceeds 100 nm, wrinkles occur in the aluminum electrode foil due to stress generated when the corrosion-resistant layer is formed, and it becomes difficult to form a flat battery electrode foil.
Accordingly, the above range (5 to 100 nm) is preferable.

In addition, as a manufacturing method of the corrosion-resistant layer of zirconium, a layer (typically an alumina layer) formed on the surface of the aluminum electrode foil is removed by plasma etching under reduced pressure, and metal aluminum is removed. After the exposure, a corrosion-resistant layer is preferably formed by a vapor phase growth method such as sputtering.
Especially, it is preferable to form a corrosion-resistant layer by sputtering. This is because it can be firmly adhered to the metal aluminum forming the aluminum electrode foil while obtaining a high film formation rate.

  Further, in the battery electrode foil described above, the corrosion-resistant layer may be a battery electrode foil having a thickness of 10 to 50 nm.

  By setting the thickness of the corrosion resistant layer to 10 nm or more, corrosion of the underlying aluminum electrode foil can be sufficiently prevented. On the other hand, when the thickness of the corrosion-resistant layer exceeds 50 nm, the resistance increases, and the capacity of the battery decreases. In addition, if the corrosion-resistant layer is made thick, it takes time and cost, so it is desirable to make it as thin as possible. Therefore, the above range is more preferable.

  Furthermore, another solution is a positive electrode plate comprising a positive electrode active material layer containing a positive electrode active material supported on the main surface of the battery electrode foil.

In the positive electrode plate of the present invention, the battery electrode foil is provided with the above-mentioned corrosion-resistant layer, and therefore has high corrosion resistance. Moreover, the electrical conductivity between the battery electrode foil and the positive electrode active material layer is also good.
Furthermore, since the corrosion-resistant layer is in contact with the aluminum electrode foil with low contact resistance, the positive electrode active material in the positive electrode active material layer supported on the main surface of the battery electrode foil has low resistance with the aluminum electrode foil. , Can exchange electronic. That is, a positive electrode plate with low resistance can be obtained, and a battery with low internal resistance can be realized.

  There is an advantage that the main surface of the battery electrode foil is not corroded even when a paste to be the positive electrode active material layer is applied at the stage of supporting the positive electrode active material layer. For this reason, the positive electrode active material layer is a positive electrode plate that stably supports the positive electrode active material layer without dropping from the battery electrode foil. Moreover, the main surface of the battery electrode foil is not corroded even when used in the battery or in contact with the electrolytic solution. Therefore, in the battery, the positive electrode active material layer should not be dropped from the battery electrode foil due to corrosion, and the positive electrode plate should be used stably without causing problems such as decomposition of the electrolytic solution. Can do.

In addition, as a positive electrode active material, the appropriate positive electrode active material in the battery system to implement | achieve can be used. Examples thereof include lithium-containing transition metal oxides such as LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiMnO ₂ , LiCo _0.5 Ni _0.5 O ₂ , and LiNi _0.7 Co _0.2 Mn _0.1 O ₂ .

  Still another solution is a battery including a power generation element including the positive electrode plate described above.

In the battery of the present invention, the power generating element includes the positive electrode plate described above. For this reason, even if a positive electrode plate contacts electrolyte solution in a battery, the main surface of battery electrode foil is not corroded. Therefore, in the battery, the positive electrode active material layer does not drop from the battery electrode foil due to corrosion, and the battery can be used stably without causing problems such as decomposition of the electrolytic solution. .
Furthermore, since the corrosion-resistant layer is in contact with the aluminum electrode foil with low contact resistance, the positive electrode active material in the positive electrode active material layer supported on the main surface of the battery electrode foil has low resistance with the aluminum electrode foil. , Can exchange electronic. That is, a positive electrode plate having a low resistance can be obtained, and a battery having a low internal resistance and capable of flowing a large current can be realized.

  Furthermore, it is preferable that the battery includes an electrolytic solution containing Li ions, and the positive electrode active material layer includes the positive electrode active material made of a Li compound.

In the Li ion battery, the potential of the positive electrode (with respect to Li ion) may rise to nearly 4.0 V, and the positive electrode battery foil is likely to be oxidized.
However, since the battery electrode foil described above is used in the battery of the present invention while being a Li-ion battery, the battery electrode foil is not oxidized during the use of the battery, and the battery is stabilized. Can be used.

Examples of the electrolytic solution include organic solvents such as ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, and diethyl carbonate, or mixed organic solvents thereof such as LiClO ₄ , LiPF ₆ , LiCF ₃ SO ₃ , LiAsF ₆ , An electrolyte solution in which a solute such as LiBF ₄ is dissolved can be used. Among these, for example, an electrolytic solution containing a chlorine-based solute such as LiClO ₄ in any one of the above organic solvents (mixed organic solvent) is more preferable because a high output can be realized in a battery having the same.

Furthermore, in the battery described above, the electrolytic solution may be a battery containing LiClO ₄ .

When LiClO ₄ is used as the electrolyte, there is an advantage that the output of the battery can be increased, but the aluminum electrode foil is corroded by the electrolyte containing LiClO ₄ even if an aluminum oxide layer is formed on the surface thereof.
In contrast, in the battery of the present invention, the electrolyte solution contains LiClO ₄ , but since the positive electrode plate provided with the battery electrode foil provided with the corrosion-resistant layer made of zirconium is used, LiClO ₄ is used. It can be used without being corroded by the electrolyte contained, and by using this LiClO ₄ , a high output battery can be realized.

  Furthermore, another solution is a vehicle equipped with the battery according to any one of the above.

  Since the vehicle according to the present invention is equipped with any of the batteries described above, the vehicle can have good running characteristics and stable performance.

  The vehicle may be a vehicle that uses electric energy from a battery for all or part of its power source. For example, an electric vehicle, a hybrid vehicle, a plug-in hybrid vehicle, a hybrid railway vehicle, a forklift, an electric Wheelchairs, electric assist bicycles, and electric scooters.

  Furthermore, another solution is a battery-mounted device on which the battery according to any one of the above-described items is mounted.

  In the battery-mounted device of the present invention, since the battery described in any of the above is mounted, the battery-mounted device having good use characteristics and stable performance can be obtained.

  The battery-equipped device may be any device equipped with a battery and using it as at least one of the energy sources. For example, a battery such as a personal computer, a mobile phone, a battery-driven electric tool, an uninterruptible power supply, etc. Various household appliances, office equipment, and industrial equipment driven by

  Furthermore, another solution is an exposure step of exposing the metal aluminum forming the aluminum electrode foil on the surface of the aluminum electrode foil, and a corrosion resistance of 5 to 100 nm thick made of metal zirconium on the exposed metal aluminum. And a corrosion-resistant layer forming step of directly forming a layer.

In general, an aluminum oxide layer is naturally formed on the surface of the aluminum electrode foil.
Therefore, in the battery electrode foil manufacturing method of the present invention, in the exposing step, the metal aluminum forming the aluminum electrode foil is exposed, and then in the corrosion-resistant layer forming step, the thickness of 5 to 100 nm is formed on the exposed metal aluminum. Zirconium is formed directly.
Thus, a battery electrode foil having a corrosion-resistant layer made of zirconium and its oxide in direct contact with the metal aluminum forming the aluminum electrode foil can be reliably produced.

  Examples of the corrosion resistant layer forming step include physical vapor deposition (PVD) methods such as sputtering, vacuum vapor deposition, and ion plating, and chemical vapor deposition methods (vapor phase growth method) such as CVD. In particular, sputtering is preferable because the film forming speed can be increased.

  Furthermore, in the method for manufacturing a battery electrode foil described above, the exposing step may be a method for manufacturing a battery electrode foil that is performed by physical etching using ions of an inert gas.

In the method for producing a battery electrode foil of the present invention, metallic aluminum is exposed on the surface of the aluminum electrode foil by physical etching with ions of an inert gas.
Since the metal aluminum is exposed by such dry etching, it is possible to easily shift to the next corrosion-resistant layer forming step and form the corrosion-resistant layer.

  Examples of the physical etching using inert gas ions include plasma etching and sputter ion beam etching. Among these, sputter ion beam etching includes a technique of performing physical etching by sputtering using an inert gas as ions.

  Furthermore, in the method for manufacturing a battery electrode foil described above, the exposure step and the corrosion-resistant layer formation step are performed in a low oxygen atmosphere where the metal aluminum exposed on the surface of the aluminum electrode foil is not substantially oxidized. Then, it is good to set it as the manufacturing method of the battery electrode foil performed continuously.

  In the method for producing a battery electrode foil according to the present invention, the exposure step and the corrosion-resistant layer forming step are continuously performed in a low-oxygen atmosphere. Therefore, the exposed metal aluminum is not oxidized and the corrosion-resistant layer is formed thereon. Can be formed directly and reliably.

An example of a low oxygen atmosphere in which metallic aluminum is not substantially oxidized includes a vacuum of 10 ⁻¹ Pa or less.

  Furthermore, another solution is a method for producing a positive electrode plate comprising a battery electrode foil and a positive electrode active material layer containing a positive electrode active material supported on the main surface of the battery electrode foil. The battery electrode foil is the battery electrode foil according to claim 1 or 2, wherein the positive electrode active material layer includes the positive electrode active material made of a Li compound, and the battery electrode foil includes the electrode foil. The main surface includes a positive electrode active material composed of the Li compound, and an aqueous active material paste using water as a solvent is applied and dried to form the positive electrode active material layer on the main surface of the battery electrode foil. A positive electrode plate manufacturing method including a positive electrode active material layer forming step.

When an aqueous active material paste containing an Li compound is used, the paste itself becomes a strong alkali due to the Li compound. When this is applied to the battery electrode foil, the aluminum forming the battery electrode foil is corroded. It is easy to form a positive electrode active material layer that generates hydrogen gas and contains many voids inside.
On the other hand, in the method for producing a positive electrode plate of the present invention, the above-described battery electrode foil, that is, the one having a corrosion-resistant layer made of zirconium and its oxide is used as the battery electrode foil. Even when the material paste is used, the battery electrode foil does not corrode and a dense positive electrode active material layer in which the generation of voids is suppressed can be formed.

(Embodiment 1)
Next, Embodiment 1 of the present invention will be described with reference to the drawings.
First, the battery 1 according to the first embodiment will be described. FIG. 1 is a perspective view of the battery 1, and FIG.
The battery 1 according to the first embodiment is a wound lithium ion secondary battery including the power generation element 20 and the electrolytic solution 60. In the battery 1, the power generation element 20 and the electrolytic solution 60 are accommodated in a rectangular box-shaped battery case 10. The battery case 10 has a battery case body 11 and a sealing lid 12 both made of aluminum. Of these, the battery case body 11 has a bottomed rectangular box shape, and an insulating film (not shown) made of resin is pasted on the entire inner surface.

  Further, the sealing lid 12 has a rectangular plate shape, and closes the opening 11 </ b> A of the battery case body 11 and is welded to the battery case body 11. Among the positive electrode current collecting member 71 and the negative electrode current collector member 72 connected to the power generation element 20 described later, the positive electrode terminal portion 71A and the negative electrode terminal portion 72A located at the tips pass through the sealing lid 12, respectively. It protrudes from the upper surface 12a. A resin insulating member 75 is interposed between the positive terminal portion 71A and the negative terminal portion 72A and the sealing lid 12 to insulate each other. Further, a rectangular plate-shaped safety valve 77 is also sealed on the sealing lid 12.

Moreover, the electrolyte 60, not shown, the ethylene carbonate (EC) and ethyl methyl carbonate (EMC), EC volume ratio: EMC = 3: a mixed organic solvent was adjusted to 7, was added LiClO ₄ as a solute, This is an organic electrolytic solution with a lithium ion concentration of 1 mol / l. Generally, in a lithium ion secondary battery, if a chlorine-based solute such as LiClO ₄ is used for the electrolyte, a higher output is possible than using a fluorine-based solute such as LiPF ₆ . For this reason, in the battery 1 of the first embodiment, a high output battery can be realized.

  The power generating element 20 is formed by winding a strip-like positive electrode plate 30 and a negative electrode plate 40 into a flat shape via a strip-like separator 50 made of polyethylene (see FIG. 1). The positive electrode plate 30 and the negative electrode plate 40 of the power generation element 20 are respectively joined to a plate-like positive current collector 71 or negative current collector 72 bent in a crank shape.

  As shown in FIG. 3, the negative electrode plate 40 of the power generation element 20 extends in a band shape in the longitudinal direction DA, and includes a negative electrode foil 42 made of copper, a first foil main surface 42 a and a second foil main surface of the negative electrode foil 42. It has the 1st negative electrode active material layer 41A and the 2nd negative electrode active material layer 41B which are each laminated on the surface 42b. The negative electrode active material layers 41A and 41B contain graphite and a binder (not shown), respectively.

  Next, the positive electrode plate 30 constituting the power generation element 20 will be described. As shown in FIG. 4, the positive electrode plate 30 has a positive foil 32 extending in a strip shape in the longitudinal direction DA, and a main surface of the positive foil 32 (first foil main surface 32a, second foil main surface 32b). Each of them has a first positive electrode active material layer 31A and a second positive electrode active material layer 31B supported thereon. Note that the first positive electrode active material layer 31A and the second positive electrode active material layer 31B are dense positive electrode active material layers that do not contain a large number of bubbles therein.

Of these, the first positive electrode active material layer 31A and the second positive electrode active material layer 31B are both positive electrode active material 31X made of LiNiO ₂ , acetylene black (AB, not shown), polytetrafluoroethylene (PTFE, not shown). And carboxymethylcellulose (CMC, not shown). The weight ratios of the first and second positive electrode active material layers 31A and 31B were both positive electrode active material 31X: AB: PTFE: CMC = 100: 10: 3: 1. The first positive electrode active material layer 31A and the second positive electrode active material layer 31B will be described in detail later. An active material paste 31P in which the above-described materials are dispersed in ion-exchanged water AQ is used as the first positive electrode active material layer 31B. Each of the first foil main surface 32a and the second foil main surface 32b is coated and dried.

  Further, the positive foil 32 is formed of an aluminum electrode foil (hereinafter simply referred to as an aluminum foil) 33 made of metal aluminum extending in a strip shape in the longitudinal direction DA, and the first foil surface 33a and the second foil surface 33b of the aluminum foil 33. The first corrosion-resistant layer 34A and the second corrosion-resistant layer 34B respectively carried on the substrate (see FIG. 5). The first corrosion-resistant layer 34A and the second corrosion-resistant layer 34B are both made of zirconium, and the layer thickness TZ in the thickness direction DT is 10 nm.

Of the aluminum foil 33, the metal aluminum forming the aluminum foil 33 is in direct contact with and carries the first corrosion-resistant layer 34A and the second corrosion-resistant layer 34B.
Due to its characteristics, metallic aluminum forms a passive film (oxide layer) made of alumina that is extremely thin (about 5 nm or less) on the surface in the atmosphere. However, the positive electrode foil 32 of Embodiment 1 removes the passive film formed on the first foil surface 33a and the second foil surface 33b of the aluminum foil 33 by a manufacturing method (exposure process) described later, Metal aluminum is exposed. And after exposure, the corrosion-resistant layers 34A and 34B are formed on the foil surfaces 33a and 33b. For this reason, the positive electrode foil 32 of this Embodiment 1 does not interpose an alumina layer, and the corrosion resistant layers 34A and 34B are in direct contact with the metal aluminum foil surfaces 33a and 33b.

By the way, in order to grasp the characteristics of the positive electrode foil 32 described above, the inventors made a prototype of a battery having the positive electrode foil and verified the capacity density of the battery at each discharge current.
Specifically, a 2032 type coin-type battery (hereinafter also referred to as battery A) using a positive electrode foil in which a first corrosion-resistant layer is directly formed on a first foil surface of an aluminum foil from which metal aluminum is exposed is used as a positive electrode plate. Was made. On the other hand, as a comparative example of battery A, a battery using a positive foil in which an alumina layer (layer thickness = 5 nm) made of aluminum oxide (Al ₂ O ₃ ) is formed on the surface of the first foil of the aluminum foil (hereinafter referred to as battery B). Also called). In addition, the positive electrode active material layer was carried on the first corrosion-resistant layer side in the battery A and the positive electrode active material layer was carried on the alumina layer side in the battery B to form a positive electrode plate. In addition, all materials except the positive electrode plate were manufactured in the same manner (for example, metallic lithium is used for the negative electrode (counter electrode)).

  A constant current discharge test was performed on each manufactured battery. Specifically, the battery was discharged at a constant current (30 C) from a full charge to a discharge end voltage (= 3.0 V) in a temperature environment of 25 ° C. In Battery A, the thickness of the first corrosion-resistant layer was evaluated for 1, 5, 10, 30, 50, 80, and 100 nm. The result of the battery A at this time is shown in FIG.

The graph of FIG. 6 shows the capacity density of each layer thickness of the first corrosion-resistant layer in the battery A. This capacity density is obtained by dividing the discharge capacity from the battery voltage at full charge (= 4.1 V) to the discharge end voltage (= 3.0 V) by the mass of the active material.
The capacity density of the battery B was 92 mAh / g, whereas the capacity density of the battery A having the corrosion-resistant layer thicknesses of 1, 5, 10, and 30 nm was 100, 98, 95, and 88 mAh, respectively. It is understood that the capacity density is / g and is larger than that of the battery B. From this result, it can be seen that if the thickness of the corrosion-resistant layer is 30 nm or less, the capacity density is larger than that of the battery B.

Furthermore, the inventors performed the following evaluation in order to examine the corrosion resistance of zirconium forming the first corrosion-resistant layer 34A and the second corrosion-resistant layer 34B.
That is, as an anticorrosion experiment, an aluminum foil (foil thickness 15 μm) having zirconium forming the first and second anticorrosive layers 34A and 34B on the foil surface was adjusted to 10 cm × 10 cm for 5 minutes in 100 ml of LiOH aqueous solution adjusted to pH 14. Soaked. In addition, it evaluated about the layer thickness of a zirconium 1,5,10,30,50,80,100nm. The volume of the corrosive gas (hydrogen gas) generated at that time was measured. The results of this corrosion resistance experiment are shown in FIG.
As a comparative experiment, an aluminum foil (foil thickness 15 μm) having an alumina layer (layer thickness 5 nm) on the surface of the foil was used as a 10 cm × 10 cm, and was immersed in the same manner as the corrosion resistance experiment. The volume of corrosive gas (hydrogen gas) was measured. The results of this comparative experiment are also shown in FIG. 7 with the zirconium film thickness being 0 nm.

  FIG. 7 is a graph showing the relationship between the layer thickness of zirconium and the amount of corrosive gas in the corrosion resistance experiment and the comparative experiment. According to this graph, when there is an alumina layer indicated by ◯ but no zirconium layer (comparative experiment), the amount of corrosive gas was 428 ml, whereas when a 1 nm zirconium layer was formed, the amount of corrosive gas was 145 ml. To decrease. Furthermore, as the zirconium layer becomes thicker, the amount of corrosive gas decreases, the layer thickness is 5 nm, the amount of corrosive gas is 25 ml, the layer thickness is 10 nm, the amount of corrosive gas is 10 ml, and the layer thickness exceeds 10 nm (for example, 20 mm or more). It can be seen that the amount of corrosive gas is 0 ml. Therefore, it can be seen that the layer thickness TZ of the corrosion-resistant layers 34A and 34B is preferably 5 nm or more, and more preferably 20 nm or more.

However, if the corrosion-resistant layer is too thick (specifically, if the layer thickness is 100 nm or more), the stress generated when the corrosion-resistant layer is formed causes wrinkles in the aluminum electrode foil, thereby forming a flat battery electrode foil. I found it difficult. In addition, when the layer thickness TZ of the corrosion-resistant layers 34A and 34B is large, the resistance increases and the capacity of the battery decreases. Therefore, it is understood that the layer thickness TZ should be 100 nm or less, more preferably 50 nm or less. I came. If the thickness TZ of the corrosion-resistant layers 34A and 34B is to be increased, it takes time and cost to form them, and there is also a desire to make them as thin as possible.
From the above, it can be seen that the thickness TZ of the corrosion resistant layers 34A and 34B formed on the aluminum foil 33 is preferably 5 to 100 nm.

  Furthermore, the amount of corrosive gas can be further reduced by setting the thickness of the corrosion-resistant layers 34A and 34B to 10 nm or more. That is, corrosion of the underlying aluminum electrode foil can be sufficiently prevented. On the other hand, if the thickness of the corrosion-resistant layer is 50 nm or less, an increase in resistance can be suppressed and a decrease in battery capacity can be suppressed. Moreover, time and cost can be reduced. Therefore, it is more preferable to use the above-mentioned range, that is, 10 to 50 nm.

  As described above, in the positive electrode foil 32 according to the first embodiment, an alkaline aqueous solution comes into contact with the positive electrode foil 32 (for example, an aqueous active material paste 31P containing a positive electrode active material made of a Li compound in which the solvent becomes a strong alkali) Even if it is applied with a positive potential), or is in a state where it is easily oxidized, it is a positive foil having good corrosion resistance that is not easily corroded.

Moreover, in the positive electrode foil 32 of the first embodiment, the metal aluminum and the corrosion resistant layers 34A and 34B are in direct contact. For this reason, compared with the case where the aluminum oxide layer is formed on the surface of the aluminum foil, the positive electrode active material layers 31A and 31B are formed on the foil main surfaces 32a and 32b (on the corrosion resistant layers 34A and 34B) of the positive electrode foil 32. When these are formed, the electrical conductivity between them can be kept good. That is, the zirconium forming the corrosion resistant layers 34A and 34B has conductivity (conductivity 40 μΩ · cm), and the corrosion resistant layers 34A and 34B are in direct contact with the metal aluminum forming the aluminum foil 33.
Therefore, in the positive electrode foil 32 of Embodiment 1, the alumina layer formed on the surface of the normal aluminum electrode foil is not interposed between the aluminum foil 33 and the corrosion resistant layers 34A and 34B. It can be set as the positive electrode foil 32 with low contact resistance between 31B.

In order to confirm this, when the inventors contacted the foil surfaces 33a and 33b of the aluminum foil 33 directly with the positive foils 32 formed with the corrosion-resistant layers 34A and 34B made of zirconium, The resistance value generated between them was measured.
Specifically, as shown in FIG. 8A, 2 samples A (corrosion-resistant layer thickness: 20 nm) obtained by joining a conductive wire LF to a ribbon-like positive foil 32 cut to a width of 2.0 cm are prepared. Two samples A are overlapped with each other so that they come into contact with each other at a contact surface of 2.0 cm × 2.0 cm (see FIG. 8B). Furthermore, the samples A are pressed together in the overlapping direction DP by a pressing device having two flat surfaces capable of clamping the contact surface. The clamping device clamps the contact surface with a clamping pressure P of 10 MPa / cm ² . Then, a current of 1.0 A is passed through each of the conducting wires LF and LF of the sample A while being clamped by the clamping device. The resistance value generated between the samples A was calculated from the voltage at that time, and it was 2.37 mΩ · cm ² .
Further, as a comparative example, Sample B formed by joining a conductive wire to an aluminum foil having an alumina layer (layer thickness: about 5 nm) on the surface is performed in the same manner as Sample A described above, and is generated between Samples B. The resistance value was calculated to be 8.44 mΩ · cm ² .

From this result, it can be seen that the resistance value between the samples A is lower than that between the samples B. That is, it can be seen that the resistance generated between the aluminum foil 33 of the positive electrode foil 32 forming the sample A and the corrosion resistant layers 34A and 34B is lower than the resistance generated between the aluminum foil forming the sample B and the alumina layer.
Thus, in the positive electrode plate 20 of Embodiment 1, the positive electrode active material 31X in the positive electrode active material layers 31A and 31B supported on the foil main surfaces 32a and 32b of the positive electrode foil 32 is low in resistance with the aluminum foil 33. , Can exchange electronic. That is, the positive electrode plate 30 having a low resistance can be obtained, and the battery 1 having a low internal resistance can be realized.

  Further, in the stage of supporting the positive electrode active material layers 31A and 31B on the positive electrode foil 32, even when the active material paste 31P to be the positive electrode active material layers 31A and 31B is applied, the foil main surfaces 32a and 32b of the positive electrode foil 32 are corroded. There are also benefits that are not. For this reason, the positive electrode active material layers 31A and 31B do not fall off from the positive electrode foil 32, and the positive electrode plate 30 carrying the positive electrode active material layers 31A and 31B can be obtained stably. In addition, the foil main surfaces 32 a and 32 b of the positive foil 32 are not corroded even when used in the battery 1 or in contact with the electrolytic solution 60. For this reason, in the battery 1, positive electrode active material layers 31A and 31B do not fall off from the positive electrode foil 32 due to corrosion, and the positive electrode plate can be stably produced without causing problems such as decomposition of the electrolytic solution 60. 30 can be used.

In the battery 1 of the first embodiment, the power generation element 20 includes the positive electrode plate 30 described above. For this reason, even if the positive electrode plate 30 contacts the electrolytic solution 60 in the battery 1, the foil main surfaces 32 a and 32 b of the positive foil 32 are not corroded. Therefore, in the battery 1, the positive electrode active material layers 31 </ b> A and 31 </ b> B are not dropped from the positive electrode foil 32 due to corrosion, and can be used stably without causing problems such as decomposition of the electrolytic solution 60. It becomes a battery that can.
Further, since the first and second corrosion-resistant layers 34A and 34B are in contact with the aluminum foil 33 with low contact resistance, the positive electrode active material layers 31A and 31B supported on the foil main surfaces 32a and 32b of the positive electrode foil 32 are used. The positive electrode active material 31X therein can exchange electrons with the aluminum foil 33 with low resistance. That is, the positive electrode plate 30 having a low resistance can be obtained, and the battery 1 having a low internal resistance and capable of flowing a large current can be realized.

In addition, since the battery 1 of Embodiment 1 is a lithium ion secondary battery, the potential of the positive electrode plate 30 (vs. Li ions) may rise to nearly 4.0 V, and the positive foil 32 of the positive electrode plate 30 may be. Is easily oxidized.
However, since the battery 1 of the first embodiment uses the positive foil 32 while being a lithium ion secondary battery, the positive foil 32 is not oxidized during the use of the battery 1, and the battery 1 is used. It can be used stably.

Moreover, since zirconium is used for the corrosion resistant layers 34A and 34B of the positive electrode plate 30, the aluminum foil 33 can be used without being corroded by the electrolytic solution 60 containing LiClO ₄ .

Next, a method for manufacturing the battery 1 according to the present embodiment will be described with reference to the drawings.
First, FIG. 9 shows a schematic view of an apparatus 100 that takes charge of the positive foil 32 and the corrosion-resistant layer forming step in the battery 1 manufacturing method. This apparatus 100 removes the alumina layer formed on the foil surfaces 33a and 33b from the foil surfaces 33a and 33b of the aluminum foil 33 by plasma etching under reduced pressure, and exposes the metal aluminum on the foil surfaces 33a and 33b. In this device, the anticorrosion layer is subsequently formed by sputtering.

  As shown in FIG. 9, the apparatus 100 includes an adjacent first decompression chamber 111, etching chamber 112, second decompression chamber 113, sputtering chamber 114, and third decompression chamber 115, as well as an unwinding portion 101 of the aluminum foil 33, A winding unit 102, a plurality of auxiliary rollers 140, and a conduction auxiliary roller 140N are provided. The aluminum foil 33 wound around the unwinding portion 101 is formed with an alumina layer having a layer thickness of about 5 nm on the foil surfaces 33a and 33b. In addition, the inlet for the aluminum foil 33 in any of the decompression chambers 111, 113, 115, the etching chamber 112, and the sputtering chamber 114 has a configuration capable of maintaining the decompression or vacuum pressure in each chamber.

Among these, the 1st decompression chamber 111, the 2nd decompression chamber 113, and the 3rd decompression chamber 115 decompress | depressurize a room | chamber interior to about 10 ^<-1 > Pa with the vacuum pump (not shown) arrange | positioned outside them. Accordingly, the etching chamber 112 and the sputtering chamber 114, which are adjacent to them, can be separated from the atmospheric pressure, so that the pressure in the etching chamber 112 and the sputtering chamber 114 can be further reduced.
The first decompression chamber 111, the second decompression chamber 113, and the third decompression chamber 115 are filled with a small amount of argon gas, and the aluminum foil 33 during the process (especially, between the exposure process and the corrosion-resistant layer formation process). The oxidation reaction (formation of alumina layer) is suppressed.

The etching chamber 112 is provided with a parallel plate type plasma etching apparatus having a flat plate-like first electrode 121 and a flat plate-like second electrode 122 parallel to the first electrode 121. Note that this chamber is filled with about 10 ⁻¹ Pa of argon gas.
Further, in the sputtering chamber 114, a sputtering apparatus having a third electrode (negative electrode) 131 that carries a target 133F made of zirconium and a flat plate-like fourth electrode (positive electrode) 132 is installed. Note that this chamber is filled with about 10 ⁻¹ Pa of argon gas. In this sputtering chamber 114, a corrosion resistant layer is formed toward the foil surfaces 33 a and 33 b of the aluminum foil 33.

First, the aluminum foil 33 is unwound from the unwinding portion 101 with the first foil surface 33 a facing upward in FIG. 9, and is moved in the longitudinal direction DA by the plurality of auxiliary rollers 140. Then, after passing through the first decompression chamber 111 decompressed in an argon atmosphere, an exposure process is performed in the etching chamber 112.
Specifically, the interior of the chamber is set to 10 ⁻¹ Pa, and Ar etching is performed by bringing the second foil surface 33 b side of the aluminum foil 33 having an alumina layer into contact with the second electrode 122 in an argon gas atmosphere. Note that the output of the first electrode 121 at this time is 200 W.
Then, the alumina layer on the 1st foil surface 33a of the aluminum foil 33 is removed from the 1st foil surface 33a, and the metal aluminum which makes the aluminum foil 33 is exposed there.

The aluminum foil 33 from which the metal aluminum is exposed moves from the etching chamber 112 to the sputtering chamber 114 through the second decompression chamber 113 decompressed in an argon atmosphere. In the sputtering chamber 114, a corrosion resistant layer forming process is performed on the aluminum foil 33.
Specifically, the interior of the room is set to 3 × 10 ⁻³ Pa, and argon gas is flowed at a flow rate of 11.5 sccm (sccm: 1.013 Pa, flow rate per unit minute at 25 ° C.) at 25 ° C. And The aluminum foil 33 is brought into contact with the fourth electrode 132, DC power is applied between the third electrode 131 and the fourth electrode 132 (200 W), and zirconium is released from the target 133F. Thus, the first corrosion-resistant layer 34A made of zirconium is formed on the first foil surface 33a of the aluminum foil 33.

After the above-described corrosion-resistant layer forming step, the aluminum foil 33 passes through the third decompression chamber 115 and is wound up by the winding unit 102.
Next, the same process is repeated for the second foil surface 33b of the aluminum foil 33 by using the apparatus 100 again. In this way, the positive foil 32 in which the first corrosion-resistant layer 34A is formed on the first foil surface 33a of the aluminum foil 33 and the second corrosion-resistant layer 34B is formed on the second foil surface 33b is produced.

In the manufacturing method of the battery 1 of Embodiment 1, the alumina layer naturally formed on the aluminum foil 33 is removed in the exposure step of the etching chamber 112 to expose the metal aluminum forming the aluminum foil 33, and then the sputtering chamber. In the corrosion-resistant layer forming process 114, the corrosion-resistant layers 34A and 34B made of zirconium are directly formed on the exposed metal aluminum.
Thus, the positive foil 32 having the corrosion resistant layers 34A and 34B that are in direct contact with the metal aluminum forming the aluminum foil 33 can be reliably manufactured.

Further, in the etching chamber 112, metal aluminum is exposed on the foil surfaces 33a and 33b of the aluminum foil 33 by etching with ions of argon gas that is an inert gas.
Since the metal aluminum is exposed by such dry etching, the corrosion resistant layers 34A and 34B can be easily formed on the aluminum foil 33 by shifting to the corrosion resistant layer forming process which is the next process.

  In the manufacturing method described above, the exposure process in the etching chamber 112 and the corrosion-resistant layer forming process in the sputtering chamber 114 are continuously performed through the second decompression chamber 113 decompressed in an argon atmosphere. That is, since the exposure process and the corrosion-resistant layer forming process are continuously performed through the etching chamber 112, the second decompression chamber 113, and the sputtering chamber 114, all of which are in a low oxygen atmosphere, the metal aluminum once exposed on the aluminum foil 33 is used. The corrosion-resistant layers 34A and 34B can be directly and reliably formed thereon without being oxidized.

Next, a hydrophilic treatment is performed on the corrosion-resistant layers 34A and 34B.
The first and second corrosion resistant layers 34A and 34B formed on the first and second foil surfaces 33a and 33b of the aluminum foil 33 may repel the aqueous active material paste 31P described below.
Therefore, a plurality of hydrophilic functional groups (for example, hydroxyl groups) are attached to the corrosion-resistant layers 34A and 34B (first and second foil main surfaces 32a and 32b) by corona discharge treatment. Specifically, in a mixed gas of nitrogen gas and hydrogen gas (volume ratio is N ₂ : H ₂ = 98: 2), the corona discharge treatment was performed with a discharge amount of 500 W · min / m ² . When corona discharge treatment is performed in an atmosphere containing oxygen gas, the oxide film becomes thick and resistance increases, but as described above, by performing this treatment in a mixed gas of nitrogen gas and hydrogen gas. It is possible to improve adhesion while preventing an increase in resistance due to the oxide film.
Accordingly, the corrosion resistant layers 34A and 34B (first and second foil main surfaces 32a and 32b) can suppress the repelling of the applied active material paste 31P. In addition to the above-described corona discharge treatment, for example, treatment using atmospheric pressure plasma or an electron beam may be performed as the hydrophilic treatment.

Next, a supporting process using the coating apparatus 200 in the positive electrode active material forming process of the battery 1 will be described.
As shown in FIG. 10, the coating apparatus 200 includes an unwinding unit 201, a die 210, a drying furnace 220, a winding unit 202, and a plurality of auxiliary rollers 240.
Among these, the die 210 includes a metal paste holding portion 211 that holds the active material paste 31P therein, and the active material paste 31P held in the paste holding portion 211 as the first foil main surface 32a of the positive foil 32. Or it has the discharge port 212 which discharges the active material paste 31P continuously toward the 2nd foil main surface 32b.
The discharge port 212 is slit-shaped, and the positive electrode foil 32 is discharged so that the active material paste 31P is discharged in a band shape on the first foil main surface 32a or the second foil main surface 32b) of the positive electrode foil 20 moving in the longitudinal direction DA. Are opened in parallel to the width direction (depth direction in FIG. 10).

The active material paste 31P held by the die 210 is made of acetylene black (AB, not shown), polytetrafluoroethylene (PTFE, not shown), and carboxymethyl cellulose (CMC, shown) in addition to the positive electrode active material 31X made of LiNiO _2. Is a fluid obtained by dispersing and kneading in ion exchange water AQ. Further, as described above, the weight ratio of the positive electrode active material 31X, AB, PTFE, and CMC contained in the active material paste 31P is the positive electrode active material 31X: AB: PTFE: CMC = 100: 10: 3: 1. . Incidentally, the active material paste 31P is for containing a positive electrode active material 31X consisting of LiNiO _2, shows a strongly alkaline.

In the drying furnace 220, hot air can be sent toward the active material paste 31 </ b> P applied to the positive foil 32. As a result, the active material paste 31P applied to the positive foil 32 is gradually dried while moving in the drying furnace 220, and when passing through the drying furnace 220, the active material paste 31P is completely dried. That is, all the water (ion exchange water AQ) in the active material paste 31P evaporates.
Further, the strip-shaped positive foil 32 is moved in the longitudinal direction DA by the plurality of auxiliary rollers 240.

  In this coating apparatus 200, first, the belt-like positive electrode foil 32 wound around the unwinding portion 201 is moved in the longitudinal direction DA, and the active material paste 31P is formed on the first foil main surface 32a of the positive electrode foil 32 by the die 210. Apply. Thereafter, the active material paste 31P is dried together with the positive electrode foil 32 in the drying furnace 220, and the single-side supported electrode foil 32K in which the uncompressed positive electrode active material layer (not shown) is supported on the first foil main surface 32a is wound up. It winds up to the part 202 once.

  Next, by using the coating apparatus 200 again, the active material paste 31P is also applied to the second foil main surface 32b of the positive foil 32 in the above-described single-side supported electrode foil 32K. Then, the active material paste 31P is completely dried in the drying furnace 220. Thus, a positive electrode plate 30B before pressing, in which an uncompressed positive electrode active material layer (not shown) is laminated on both foil main surfaces 32a and 32b of the positive electrode foil 32, is manufactured.

As described above, since the aqueous active material paste 31P itself becomes a strong alkali, when it is applied to, for example, an aluminum foil, the metal aluminum forming the aluminum foil is corroded to generate hydrogen gas, It is easy to form a positive electrode active material layer containing many voids.
On the other hand, in the manufacturing method of the battery 1 of the first embodiment, since the positive foil 32 provided with the corrosion-resistant layers 34A and 34B made of zirconium is used, the positive foil is used even when the above-described aqueous active material paste 31P is used. Dense positive electrode active material layers 31A and 31B in which 32 does not corrode and suppress the generation of voids can be formed.

Next, FIG. 11 shows a press cutting process using the press device 300 in the positive electrode active material forming process of the battery 1.
The press device 300 includes an unwinding unit 301, a press roller 310, a winding unit 302, a cutting blade 330, and a plurality of auxiliary rollers 320. And in this press apparatus 300, the above-mentioned positive electrode plate 30 compressed in the thickness direction is obtained by passing the above-mentioned positive electrode plate 30B before press from the unwinding part 301 between the two press rollers 310. Can do. Thereafter, the center is cut by the cutting blade 330 and divided into two, and then the positive electrode plate 30 is wound by the two winding portions 302.

  After the press cutting process described above, the produced positive electrode plate 30 is wound together with the separately prepared negative electrode plate 40 via the separator 50 to form the power generation element 20. Further, the positive electrode current collecting member 71 and the negative electrode current collecting member 72 are welded to the power generation element 20, inserted into the battery case main body 11, the electrolyte solution 60 is injected, and then the battery case main body 11 is sealed with the sealing lid 12 by welding. . Thus, the battery 1 is completed (see FIG. 1).

(Embodiment 2)
A vehicle 400 according to the second embodiment includes a battery pack 410 including a plurality of the batteries 1 described above. Specifically, as shown in FIG. 12, vehicle 400 is a hybrid vehicle that is driven by using engine 440, front motor 420, and rear motor 430 together. The vehicle 400 includes a vehicle body 490, an engine 440, a front motor 420, a rear motor 430, a cable 450, an inverter 460, and a battery pack 410 having a rectangular box shape. Among these, the battery pack 410 accommodates a plurality of the batteries 1 according to the first embodiment described above inside a rectangular battery case 411.

  For this reason, in the vehicle 400 according to the second embodiment, since the battery 1 described above is mounted, it is possible to provide a vehicle with good running characteristics and stable performance.

(Embodiment 3)
Further, the hammer drill 500 of the third embodiment is mounted with the battery pack 510 including the battery 1 described above, and is a battery-mounted device having a battery pack 510 and a main body 520 as shown in FIG. Battery pack 510 is housed in bottom 521 of main body 520 of hammer drill 500.

  For this reason, in the hammer drill 500 concerning this Embodiment 3, since the battery 1 of the above-mentioned description is mounted, it can be set as the battery mounting apparatus of a favorable use characteristic and the stable performance.

In the above, the present invention has been described with reference to the first, second, and third embodiments. However, the present invention is not limited to the above-described embodiments and the like, and can be appropriately modified and applied without departing from the gist thereof. Needless to say, you can.
For example, in Embodiment 1 or the like, the battery case of the battery is a rectangular container, but may be a cylindrical container or a laminate container. In Embodiment 1 and the like, the alumina layer of the aluminum foil 22 is removed by plasma etching in the production of the battery electrode foil. However, for example, the alumina layer may be removed using sputter ion beam etching. In this case, there is a method of performing physical etching by sputtering using an inert gas as ions.
In the production of battery electrode foils, a corrosion-resistant layer was formed by sputtering. For example, other than sputtering, physical vapor deposition (PVD) methods such as vacuum vapor deposition and ion plating, and chemical vapor deposition methods such as CVD (gas vapor deposition) It is also possible to use a phase growth method.

In Embodiment 1 or the like, the cathode active material 31X having LiNiO ₂ is used. For example, LiCoO ₂ , LiMn ₂ O ₄ , LiMnO ₂ , LiCo _0.5 Ni _0.5 O ₂ , LiNi _0.7 Co _0.2 Mn other than LiNiO ₂ are used. A lithium-containing transition metal oxide such as _0.1 O ₂ may be used.
Further, in Embodiment 1 and the like, LiClO ₄ is used as the solute of the electrolytic solution 60. However, for example, LiPF ₆ , LiCF ₃ SO ₃ , LiAsF ₆ , LiBF _{4, and the} like may be used.

3 is a perspective view of a battery according to Embodiment 1, Modification 1 and Modification 2. FIG. 3 is a cross-sectional view of a battery according to Embodiment 1, Modification 1 and Modification 2. FIG. 3 is a perspective view of a negative electrode plate according to Embodiment 1. FIG. It is a perspective view of the positive electrode plate of Embodiment 1, Modification 1, and Modification 2. FIG. 6 is an enlarged end view of the positive electrode plate according to Embodiment 1 and Modification 1 (A portion in FIG. 4). It is a graph which shows the relationship between a capacity density and a battery voltage. It is a graph which shows the relationship between a capacity density and a battery voltage. It is explanatory drawing which shows the resistance value measurement between positive electrode foils. It is explanatory drawing of the exposure process of Embodiment 1, and a corrosion-resistant layer formation process. FIG. 3 is an explanatory diagram of a positive electrode active material forming step of Embodiment 1. FIG. 3 is an explanatory diagram of a positive electrode active material forming step of Embodiment 1. It is explanatory drawing of the vehicle concerning Embodiment 2. FIG. It is explanatory drawing of the hammer drill concerning Embodiment 3. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Battery 20 Power generation element 30 Positive electrode plate 31A 1st positive electrode active material layer (positive electrode active material layer)
31B Second positive electrode active material layer (positive electrode active material layer)
31P active material paste (aqueous active material paste)
31X Positive electrode active material 32 Positive electrode foil (battery electrode foil)
33 Aluminum foil (Aluminum electrode foil)
33a First foil surface (surface of (aluminum electrode foil))
33b Second foil surface (surface of aluminum electrode foil)
34A First corrosion resistant layer (corrosion resistant layer)
34B Second corrosion resistant layer (corrosion resistant layer)
60 Electrolyte 400 Vehicle 500 Hammer drill (Battery-equipped equipment)
AQ ion exchange water (water)
TZ layer thickness (thickness of (corrosion resistant layer))

Claims (12)

Aluminum electrode foil,
A battery electrode foil comprising a corrosion resistant layer having a thickness of 5 to 100 nm made of metal zirconium formed on the surface of the aluminum electrode foil and in direct contact with the metal aluminum forming the aluminum electrode foil. The battery electrode foil according to claim 1,
The corrosion-resistant layer is a battery electrode foil having a thickness of 10 to 50 nm. The battery electrode foil according to claim 1 or 2,
A positive electrode plate comprising: a positive electrode active material layer including a positive electrode active material supported on a main surface of the battery electrode foil. A battery comprising a power generation element including the positive electrode plate according to claim 3. The battery according to claim 4,
An electrolyte containing Li ions;
The positive electrode active material layer is a battery including the positive electrode active material made of a Li compound. The battery according to claim 5,
The battery is a battery comprising LiClO ₄ . A vehicle equipped with the battery according to any one of claims 4 to 6. The battery mounting apparatus which mounts the battery of any one of Claims 4-6. An exposing step of exposing the metal aluminum forming the aluminum electrode foil on the surface of the aluminum electrode foil;
A corrosion-resistant layer forming step of directly forming a corrosion-resistant layer having a thickness of 5 to 100 nm made of metal zirconium on the exposed metal aluminum. It is a manufacturing method of the electrode foil for batteries according to claim 9,
The method of manufacturing a battery electrode foil, wherein the exposing step is performed by physical etching with an inert gas ion. It is a manufacturing method of the electrode foil for batteries according to claim 10,
A method for producing an electrode foil for a battery, wherein the exposing step and the corrosion-resistant layer forming step are continuously performed in a low oxygen atmosphere in which the metal aluminum exposed on the surface of the aluminum electrode foil is not substantially oxidized. Battery electrode foil;
A positive electrode active material layer comprising a positive electrode active material carried on the main surface of the battery electrode foil, and a positive electrode plate manufacturing method comprising:
The battery electrode foil is the battery electrode foil according to claim 1 or 2,
The positive electrode active material layer includes the positive electrode active material made of a Li compound,
On the main surface of the battery electrode foil, a water-based active material paste containing a positive electrode active material composed of the Li compound and containing water as a solvent is applied and dried on the main surface of the battery electrode foil. A positive electrode plate manufacturing method comprising a positive electrode active material layer forming step of forming the positive electrode active material layer.

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