KR20090103838A - Method of manufacturing electrode, electrical storage device, and intermediate laminated material - Google Patents

Abstract

PURPOSE: A method for manufacturing an electrode, an electrical storage device, and an intermediate laminated material are provided to increase a sending speed when painting electrode slurry by painting electrode slurry on a current collector laminated unit. CONSTITUTION: A method for manufacturing an electrode including a current collector which is opened comprises the steps of: forming a current collector laminated unit(30) by laminating a plurality of current collector materials(31,32); forming a protective layer with desired patterns on the surface of the current collector laminated unit; performing etching process to the current collector laminated unit formed with the protective layer; forming through holes(20a,23a) of current collector material; plating electrode slurry on the surface of the current collector laminated unit in which the through hole is formed; separating the current collector material plated with the electrode slurry from the current collector laminated unit; and painting the electrode slurry on the unplated surface of current collector material separated from the current collector laminated unit.

Description

Production method of electrode, power storage device, and intermediate | middle laminated material {METHOD OF MANUFACTURING ELECTRODE, ELECTRICAL STORAGE DEVICE, AND INTERMEDIATE LAMINATED MATERIAL}

This invention relates to the manufacturing method of the electrode provided with the perforated electrical power collector, the electrical storage device in which the electrode provided with the perforated electrical power collector is built-in, the intermediate | middle laminated material as an object in the manufacturing process of an electrode, etc.

Electric vehicles, hybrid vehicles, etc., are equipped with electrical storage devices, such as a lithium ion battery and a lithium ion capacitor. When manufacturing the electrode embedded in an electrical storage device, the electrode slurry which contains an active material in current collector materials, such as metal foil, is coated. And it is common to dry an electrode slurry and to form an electrode mixture layer by passing a drying furnace conveying a collector material in a horizontal direction.

Moreover, in order to improve the energy density of an electrical storage device, the electrical storage device which brought the metal lithium foil and the cathode into electrochemical contact is proposed. In this power storage device, lithium ions can be doped to the cathode in advance. As a result, the potential of the cathode can be lowered, the capacitance of the cathode can be increased, and the energy density of the power storage device can be improved. In addition, in order to uniformly dope lithium ions with respect to the several negative electrode laminated | stacked, the through-hole for passing lithium ion is formed in the electrical power collector of each electrode (for example, refer patent document 1).

By the way, when coating an electrode slurry on the collector material in which the through-hole was formed, there exists a possibility that an electrode slurry may pass through a through-hole and escape to the back surface side of a collector material. In this way, when the electrode slurry exits to the back surface side of the current collector material, the electrode slurry adheres to the guide roller supporting the current collector material. Therefore, a manufacturing method is proposed in which the electrode slurry is coated while pulling up the current collector material in the vertical direction. According to this manufacturing method, since the guide roller is not necessary in the pulling-up process of the current collector material, it becomes possible to prevent adhesion of the electrode slurry to the guide roller. Moreover, the electrical storage device which formed the through-hole with respect to a collector material small and prevents an electrode slurry from escaping to the back surface side of a collector material is also proposed (for example, refer patent document 2).

In addition, Patent Literature 3 discloses a configuration in which metal foils provided on both sides by sandwiching an adhesive layer or an insulating layer are etched with a resist of a predetermined pattern to open a hole.

[Patent Document 1] Japanese Patent No. 3485935

[Patent Document 2] Japanese Unexamined Patent Publication No. 2007-141897

[Patent Document 3] Japanese Patent No. 3411514

However, raising the current collector material in the vertical direction causes a decrease in the conveying speed, and thus there is a problem that the productivity of the electrode is lowered. That is, the current collector material must be pulled up in the vertical direction until the electrode slurry coated on the current collector material is dried. However, since the current collector material may be broken by its own weight, there is a limit to the height of the current collector material being raised. In accordance with the restriction of the pulling height, there is a limitation in the height dimension of the drying furnace for drying the electrode slurry. In order to dry an electrode slurry by such a short drying furnace, it is necessary to lower the conveyance speed of an electrical power collector material. In this way, pulling up the current collector material in the vertical direction reduces the productivity of the electrode and increases the manufacturing cost of the electrode.

In addition, when through-holes are formed small so that an electrode slurry does not escape on the back surface side of a collector material, it is possible to coat an electrode slurry, conveying a collector material horizontally. However, since the strength of the current collector material in which the through holes are formed is lower than that of the current collector material without the through holes, the conveyance speed of the current collector having the through holes tends to be lowered. Thus, even when horizontal conveyance is enabled by the small diameter of a through hole, it is difficult to improve productivity of an electrode compared with the electrical power collector material which does not have a through hole. In addition, since the through-hole of the current collector becomes small, the doping rate of lithium ions may be lowered when doping lithium ions with a negative electrode. This slowing down of the movement speed will lead to prolongation of the doping operation of lithium ions to the negative electrode. The prolongation of this doping operation has been a factor of lowering the productivity of the power storage device and raising the manufacturing cost of the power storage device.

Moreover, as a method of processing through-holes in a current collector material, there are etching processes such as mechanical processing and chemical processing such as presses, but it is preferable to perform etching processing in terms of quality. However, when performing an etching process, it is common to form the resist layer of a predetermined pattern on the surface of each metal foil, and to form a resist layer on the whole back surface of each metal foil. As described above, forming a resist layer for each sheet of metal foil and performing an etching process became a factor of lowering the productivity of the current collector and lowering the productivity of the electrode.

An object of the present invention is to improve the productivity of an electrode including a current collector having a hole.

The manufacturing method of the electrode of this invention is a manufacturing method of the electrode provided with the electrical power collector which perforated, The electrical power collector lamination process of laminating | stacking a some electrical power collector material, and forming an electrical power collector laminated unit, A protective layer forming step of forming a protective layer of a predetermined pattern on a surface, an etching process of etching the current collector stacking unit in which the protective layer is formed, and forming a through hole in each of the current collector material; and A first coating step of coating an electrode slurry on a surface of the current collector stacking unit in which a through hole is formed, a current collector peeling step of peeling the current collector material coated with the electrode slurry from the current collector stacking unit, and the current collector And a second coating step of coating the electrode slurry on the uncoated surface of the current collector material separated from the entire lamination unit.

In the electrode manufacturing method of the present invention, in the current collector stacking step, a blocking layer is interposed between the current collector materials, and in the protective layer forming step, both of one surface and the other surface of the current collector stacking unit are provided. The protective layer of a predetermined pattern is formed, and in the etching step, the through holes are formed in each of the current collector material from both of one surface and the other surface of the current collector stacking unit.

In the electrode manufacturing method of the present invention, a plurality of the current collector materials are directly laminated in the current collector stacking step, and in the protective layer forming step, a blocking layer is formed on one entire surface of the current collector stacking unit. And forming the protective layer in a predetermined pattern on the other side of the current collector stacking unit, and in the etching process, forming the through holes in each of the current collector material from the other side of the current collector stacking unit. It features.

In the manufacturing method of the electrode of this invention, in the manufacturing method of the electrode of any one of the above, the through-holes formed in each of the said some laminated current collector material are provided facing each other, and the through-holes provided facing each other The spherical surface is characterized by being shifted from each other.

The manufacturing method of the electrode of this invention is the manufacturing method of the electrode of any one of this invention WHEREIN: The through-hole formed in each of the said some collector material laminated | stacked prevents the fall of an electrode mixture layer in the inner surface of the said through-hole. A means is provided.

In the manufacturing method of the electrode of this invention, in the manufacturing method of the electrode of this invention, the said fall prevention means is the opening surface of the through-hole end from the coating side of an electrode slurry to a penetration direction parallel to the said opening surface. It is characterized by making it smaller than the other opening surface in the said through hole cut into the surface.

In the manufacturing method of the electrode of this invention, in the manufacturing method of the electrode of this invention, the said fall prevention means is toward the opening surface of the other end of the said through hole from the opening surface of the coating side of the electrode slurry of the said through hole. The installed end is characterized in that the tapered taper.

The electrical storage device of this invention is an electrical storage device in which the electrode containing the perforated electrical power collector is built-in, The said electrode is manufactured using the manufacturing method of the electrode as described in any one of Claims 1-7. It is done.

In the power storage device of the present invention, the power storage device is a lithium ion capacitor.

In the power storage device of the present invention, the power storage device is a lithium ion battery.

The intermediate | middle laminated material of this invention is an intermediate | middle laminated material as a thing currently being manufactured in the manufacturing process of an electrode, Comprising: It is an electrical power collector material containing a some through hole, and is provided in one surface side of the said electrical power collector material, and closes the said through hole. And a blocking layer and an electrode mixture layer provided on the other surface side of the current collector material.

In the intermediate | middle laminated material of this invention, in the intermediate | middle laminated material of the said structure, the said electrical power collector material is laminated | stacked on both surfaces of the said barrier layer.

In the intermediate | middle laminated material of this invention, in the intermediate | middle laminated material of the said structure, the said electrical power collector material is laminated | stacked on one side of the said blocking layer, It is characterized by the above-mentioned.

As for the intermediate | middle laminated material of this invention, in the intermediate | middle laminated material of this invention of the said base material, the said electrical power collector material is provided in multiple numbers by opposing each other with the said blocking layer interposed, and is formed in each of the said electrical power collector material provided oppositely. The opening faces of the through-holes facing the blocking layer are shifted from each other.

The intermediate | middle laminated material of this invention is the intermediate | middle laminated material of this invention of the said base material WHEREIN: It is characterized in that the through-hole is provided with the fall prevention means of an electrode mixture layer in the inner surface.

The intermediate | middle laminated material of this invention is the intermediate | middle laminated material of this invention of the said base material, The said fall prevention means is the other which cut | disconnected the opening surface which faces the said blocking layer side of the said through hole to the surface parallel to the said opening surface. It is characterized by smaller than the opening surface.

The intermediate | middle laminated material of this invention is the intermediate | middle laminated material of this invention of the said base material WHEREIN: The said fall prevention means is a taper-shaped tapered edge provided in the said through-hole toward the said blocking layer.

In the present invention, since a plurality of current collector materials are subjected to etching treatment, the productivity of the current collector having a perforated hole can be improved, and the productivity of the electrode can be improved. In addition, since the electrode slurry is coated on the current collector stacking unit in which a plurality of current collector materials are laminated, the conveyance speed at the time of coating the electrode slurry can be increased, and the productivity of the electrode can be improved.

1 is a perspective view illustrating a power storage device.

2 is a cross-sectional view schematically showing the internal structure of the power storage device taken along the line A-A in FIG.

3 is a cross-sectional view partially showing an internal structure of a power storage device.

4 is a flowchart illustrating a method of manufacturing an electrode, which is one embodiment of the present invention.

5A to 5D are schematic diagrams showing states of electrodes in respective manufacturing steps.

6A to 6D are schematic diagrams showing states of electrodes in respective manufacturing steps.

7 is a schematic diagram illustrating an example of a coating drying apparatus.

8 is a flowchart illustrating a method of manufacturing an electrode, which is another embodiment of the present invention.

9A to 9E are schematic diagrams showing states of electrodes in respective manufacturing steps.

10A to 10C are schematic diagrams showing states of electrodes in respective manufacturing steps.

11A to 11C are schematic diagrams showing the state of an electrode in each manufacturing step.

12A to 12E are schematic diagrams illustrating respective manufacturing steps when forming through holes in the current collector material.

It is a flowchart which shows the manufacturing method of the electrode which is another embodiment of this invention.

14 is a schematic view showing an example of a polymerization rolling device.

FIG. 15A is an explanatory diagram showing a case where the opposing opening faces coincide, and (B) is a case where the opposing opening faces are shifted.

FIG. 16A shows a planar pattern of an opening surface, and FIG. 16B is an explanatory diagram showing a state of positional shift of an opposing opening surface.

17 is an explanatory diagram showing the overlap ratio of an opening surface;

18 is an explanatory diagram showing a case where opposing opening surfaces coincide with each other;

19A to 19C are explanatory diagrams showing a method of shifting positions of opposing opening surfaces.

20A to 20C are explanatory diagrams showing a method of shifting positions of opposing opening surfaces.

21 (A) and 21 (B) are explanatory diagrams showing a method of shifting positions of opposing opening surfaces.

22A and 22B are explanatory diagrams showing a method of shifting positions of opposing opening surfaces.

Fig. 23 is an explanatory diagram showing a method of shifting positions of opposing opening surfaces.

FIG. 24A is an explanatory diagram showing a modification in the case where the opposing opening faces coincide with each other, and (B) is the misalignment of the opposing opening faces.

FIG. 25 is a schematic view showing a state in which an electrode slurry is filled in a through hole in FIG. 6. FIG.

FIG. 26 is a schematic view showing a state in which an electrode slurry is filled in a through hole in FIG. 10. FIG.

FIG. 27 is a schematic view showing a state in which an electrode slurry is filled in a through hole in FIG. 11; FIG.

28A and 28B are cross-sectional explanatory diagrams showing a through hole shape in which the electrode mixture layer easily falls off;

29A to 29C are explanatory diagrams showing a fall prevention means provided in a through hole and a modification thereof;

30A to 30D are explanatory diagrams illustrating an example of the dropout preventing means and its function;

<Code description>

13: positive electrode (electrode), 14: negative electrode (electrode), 20: positive electrode current collector (perforated current collector), 20a: through hole, 21: positive electrode mixture layer (electrode mixture layer), 23: negative electrode current collector (hole) The perforated current collector), 23a: through hole, 24: negative electrode mixture layer (electrode mixture layer), 30: current collector laminated unit, 30a: one side (surface), 31: current collector material, 32: current collector material, 33 : Film material (blocking layer), 34: resist layer (protective layer), 37: uncoated surface, 41: intermediate laminated material, 42: intermediate laminated material, 50: current collector laminated unit, 50b: other surface (surface), 51: resist layer (protective layer), 52: intermediate laminated material, 53: uncoated surface, α: opening surface, α1: opening surface, β: opening surface, β1: opening surface, θ: release side opening surface, θ1: filling Side opening face, θ2: non-dropping side opening face, D: thickness, d: thickness

(Embodiment 1)

1 is a perspective view illustrating the power storage device 10. FIG. 2 is a sectional view schematically showing the internal structure of the electrical storage device 10 taken along the line A-A of FIG. 1. As shown in FIG. 1 and FIG. 2, the electrode lamination unit 12 is accommodated in the laminated film 11 which is an exterior container. The electrode stacking unit 12 is composed of an anode (electrode) 13 and a cathode (electrode) 14 which are alternately stacked. The separator 15 is provided between the positive electrode 13 and the negative electrode 14. In the outermost part of the electrode stacking unit 12, a lithium electrode 16 is disposed to face the cathode 14. The separator 15 is provided between the cathode 14 and the lithium electrode 16. The three-electrode lamination unit 17 is constituted by these electrode lamination units 12 and the lithium electrode 16. In addition, the electrolyte solution is injected into the laminate film 11. This electrolyte solution is comprised by the aprotic organic solvent containing a lithium salt.

3 is a cross-sectional view partially showing an internal structure of the power storage device 10. As shown in FIG. 3, the positive electrode 13 has a positive electrode current collector (perforated current collector) 20 in which a plurality of through holes 20a are formed. The positive electrode mixture layer 21 is coated on the positive electrode current collector 20. In addition, the positive electrode current collector 20 is provided with a terminal weld 20b extending convexly. The plurality of terminal welding portions 20b are joined to each other in an overlapped state. The positive electrode terminal 22 is joined to the terminal welding portion 20b joined to each other. Similarly, the negative electrode 14 has a negative electrode current collector (perforated current collector) 23 in which a plurality of through holes 23a are formed. The negative electrode current collector 23 is coated with a negative electrode mixture layer 24. In addition, the negative electrode current collector 23 is provided with a convex terminal weld 23b. The plurality of terminal welding portions 23b are joined to each other in an overlapped state. In addition, the negative electrode terminal 25 is joined to the terminal welding part 23b joined together.

The positive electrode mixture layer 21 contains activated carbon as a positive electrode active material. This activated carbon can be reversibly doped and dedoped with lithium ions and anions. The negative electrode mixture layer 24 includes a polyacene organic semiconductor (PAS) as the negative electrode active material. In this PAS, lithium ions can be reversibly doped and dedoped. Thus, by using activated carbon as the positive electrode active material and PAS as the negative electrode active material, the electrical storage device 10 shown functions as a lithium ion capacitor. In addition, in this specification, doping means occlusion, support, adsorption | suction, intestine, etc. That is, doping means the state which lithium ion etc. enter into a positive electrode active material or a negative electrode active material. In addition, de-doping means release | release and departure | release. That is, de-doping means the state which lithium ion etc. come out from a positive electrode active material or a negative electrode active material.

As described above, the lithium electrode 16 is built in the power storage device 10. This lithium electrode 16 has a lithium electrode current collector 26 joined to the negative electrode current collector 23. In addition, metal lithium foil 27 as an ion supply source is pressed to the lithium electrode current collector 26. Therefore, the metallic lithium foil 27 and the negative electrode mixture layer 24 are in a state of being connected through the lithium electrode current collector 26 and the negative electrode current collector 23. In this manner, the cathode 14 and the lithium electrode 16 have a structure in which they are electrically connected. Therefore, by injecting the electrolyte solution into the laminate film 11, lithium ions are doped (hereinafter referred to as pre-doping) from the lithium electrode 16 to the cathode 14.

Thus, by pre-doping lithium ion to the cathode 14, it becomes possible to reduce a cathode potential. This makes it possible to increase the cell voltage of the electrical storage device 10. In addition, it is possible to discharge the positive electrode 13 at a high capacity due to the decrease in the negative electrode potential, thereby increasing the cell capacity (discharge capacity) of the power storage device 10. In addition, by pre-doping lithium ions to the cathode 14, it becomes possible to increase the capacitance of the cathode 14. This makes it possible to increase the capacitance of the electrical storage device 10. In this manner, the cell voltage, the cell capacity, and the electrostatic capacitance of the power storage device 10 can be increased, so that the energy density of the power storage device 10 can be improved. In order to increase the capacity of the power storage device 10, the metal lithium foil 27 is formed so that the anode potential after the short circuit of the anode 13 and the cathode 14 is 2.0 V (Li / Li + pair) or less. It is desirable to set the amount.

In addition, through holes 20a and 23a are formed in the positive electrode current collector 20 and the negative electrode current collector 23. For this reason, it becomes possible to move the lithium ion discharge | released from the lithium electrode 16 to a lamination direction. As a result, it is possible to smoothly pre-dope lithium ions to all the stacked negative electrodes 14.

Next, the manufacturing method of the positive electrode 13 and the negative electrode 14 is demonstrated. In the following description of the manufacturing method, the positive electrode 13 and the negative electrode 14 are described as electrodes so that the manufacturing method of the positive electrode 13 and the manufacturing method of the negative electrode 14 will be described in an integrated manner. In addition, in description of a manufacturing method, the positive electrode mixture layer 21 and the negative electrode mixture layer 24 are described as an electrode mixture layer. 4 is a flowchart illustrating a method of manufacturing the electrode, which is one embodiment of the present invention. 5 and 6 are schematic diagrams showing the state of the electrode in each manufacturing process.

As shown in FIG. 4, in step S101, a current collector stacking step of forming the current collector stacking unit 30 is performed. In this current collector lamination process, as shown to FIG. 5 (A), the long collector materials 31 and 32 which consist of metal foil are prepared, and the long film material 33 is provided as a barrier layer. Is ready. Then, by sandwiching the film material 33 by the pair of current collector materials 31 and 32, the current collector stacking unit 30 made of the current collector materials 31 and 32 and the film material 33 is formed. . In addition, when manufacturing the positive electrode 13, for example, aluminum foil is used as the current collector materials 31 and 32. On the other hand, when manufacturing the negative electrode 14, for example, copper foil is used as the current collector materials 31 and 32. In addition, as the film material 33, what has resistance to the etching liquid mentioned later is used. In addition, as the film material 33, in order to respond to the electrical power collector peeling process mentioned later, it is preferable to use a non-adhesive film or a peelable film. For example, it is possible to use Riva alpha (registered trademark, Nitto Denko Co., Ltd.) as the film to be peeled off by heating. In addition, Panaprotect (registered trademark, Panak Corporation) can be used as the non-adhesive film.

As shown in FIG. 4, in the following step S102, the resist printing process (protective layer formation process) which forms the resist layer 34 as a protective layer in the collector laminated unit 30 is performed. In this resist printing process, as shown in FIG. 5 (B), resist ink is printed on both of one surface 30a and the other surface 30b of the current collector stacking unit 30 in a predetermined pattern. . Thereby, the resist layer 34 of a predetermined pattern is formed in both the one surface 30a and the other surface 30b of the collector laminated unit 30. As shown in FIG. In the resist printing step, although the resist ink is printed by gravure printing, screen printing, or the like, when the film material 33 as the barrier layer is present, both patterns are not required to match. In addition, as a resist ink, if it has resistance to the etching liquid mentioned later, a general thing can be used. Moreover, as resist ink, what can melt | dissolve and remove with an alkali solvent etc. is preferable.

In addition, in the above description, although the resist layer 34 is formed using liquid resist ink, you may make it adhere | attach the dry film resist previously filmed. For example, it is possible to use FXR, FX900, etc. made by Dupont MRC Dry Film Co., Ltd. as a dry film resist. In the case of using a dry film resist, a resist layer 34 having a predetermined pattern is formed in the current collector stacking unit 30 by performing exposure and development treatments on the adhered dry film resist.

As shown in FIG. 4, in the following step S103, the etching process of forming through-holes 20a and 23a in the collector laminated unit 30 is performed. In this etching process, as shown to FIG. 5C, the current collector laminated unit 30 is etched using the resist layer 34 as a mask. As a result, a plurality of through holes 20a and 23a are provided for the respective current collector materials 31 and 32 from both sides of one surface 30a and the other surface 30b of the current collector stacking unit 30. Is formed. The etching liquid used for this etching process is suitably selected according to the material of the collector materials 31 and 32. FIG. As described above, when aluminum foil or copper foil is used as the current collector materials 31 and 32, it is possible to use ferric chloride aqueous solution, caustic soda, hydrochloric acid and the like as the etching solution.

As shown in FIG. 4, in the following step S104, the resist removal process which removes the resist layer 34 from the collector laminated unit 30 is performed. In this resist removal process, as shown to FIG. 5D, the resist layer 34 which protected non-etching parts other than the through hole 20a, 23a is removed from the collector laminated unit 30. As shown in FIG. In the case of using an alkali dissolving resist ink, it is possible to remove the resist layer by using an aqueous solution of sodium hydroxide after etching by washing with hydrochloric acid or the like. In addition, by repeatedly washing, neutralizing and washing, the current collector materials 31 and 32 having the through holes 20a and 23a are formed in the state where the film material 33 is sandwiched.

As described above, since the etching treatment is performed on the plurality of current collector materials 31 and 32 at the same time, the manufacturing cost of the positive electrode current collector 20 or the negative electrode current collector 23 in which the through holes 20a and 23a are formed is reduced. It becomes possible to cut down drastically. Moreover, the film material 33 which interrupts etching liquid is interposed between the collector materials 31 and 32, and each of the collector materials 31 and 32 is subjected to the etching process from one surface side. As a result, it is not necessary to match the pattern of the resist layer 34 formed on both surfaces of the current collector stacking unit 30, thereby reducing the manufacturing cost of the positive electrode current collector 20 or the negative electrode current collector 23. It becomes possible.

Subsequently, as shown in FIG. 4, in step S105, the 1st slurry coating process (1st coating process) which forms the 1st electrode mixture layer 35 in the electrode A comprised by one electrical power collector material 31. ) Is carried out. In this first slurry coating step, as shown in FIG. 6A, an electrode slurry is coated on one surface (surface) 30a of the current collector stacking unit 30. Moreover, you may coat so that an electrode slurry may be filled in the through hole 20a, 23a. And the electrode mixture layer 35 is formed on the surface 30a of the collector laminated unit 30 by drying this electrode slurry. Thus, in the manufacturing process of an electrode, the intermediate | middle laminated material 41 as a manufacturing object provided with the film material 33 which closes the through-holes 20a and 23a is formed. This intermediate | middle laminated material 41 is an electrical power collector material 31 in which the through-holes 20a and 23a were formed, the film material 33 provided in one surface side of the electrical power collector material 31, and the electrical power collector material 31 It has the electrode mixture layer 35 provided in the other surface side of (). Here, FIG. 7 is a schematic diagram which shows an example of the coating drying apparatus 100. As shown in FIG. As illustrated in FIG. 7, the current collector stacking unit 30 after etching released from the roll 101 is guided to coating portions 102 such as a die coater. In this coating part 102, an electrode slurry is coated on the current collector stacking unit 30. In order to dry the coated electrode slurry, the current collector stacking unit 30 is passed through the drying furnace 103 while being conveyed in the horizontal direction.

As described above, the film material 33 is provided between the current collector materials 31 and 32. Therefore, even when the electrode slurry is coated on the current collector materials 31 and 32 having the through holes 20a and 23a, the electrode slurry passes through the through holes 20a and 23a and the rear surface of the current collector stacking unit 30 is used. Do not exit to the side. Therefore, the electrode slurry is not attached to the guide roller 104 or the like, and the current collector stacking unit 30 can be transported in the horizontal direction. This makes it possible to set the drying furnace 103 longer than the coating method of pulling up the current collector material in the vertical direction. Therefore, the conveyance speed of the collector materials 31 and 32 can be raised, and the productivity of an electrode can be improved. Further, in the current collector materials 31 and 32 in which the through holes 20a and 23a are formed, the strength is lower than that of the current collector material without the through holes. For this reason, it has become difficult to raise the conveyance speed of the collector materials 31 and 32 in which the through-holes 20a and 23a were formed. On the other hand, it is possible to raise the intensity | strength by superimposing current collector materials 31 and 32 across the film material 33. Thereby, the conveyance speed of the collector materials 31 and 32 can be raised, and it becomes possible to improve productivity of an electrode.

Subsequently, as shown in FIG. 4, in step S106, a first slurry coating step of forming the first electrode mixture layer 36 is performed on the electrode B formed of the other current collector material 32. In this 1st slurry coating process, as shown to FIG. 6 (B), an electrode slurry is coated on the other surface (surface) 30b of the electrical power collector laminated unit 30 which inverted top and bottom. Moreover, you may coat so that an electrode slurry may be filled in the through hole 20a, 23a. Then, the electrode mixture layer 36 is formed on the surface 30b of the current collector stacking unit 30 by drying the electrode slurry. Thus, in the manufacturing process of an electrode, the intermediate | middle laminated material 42 as a manufacturing object provided with the film material 33 which closes the through-holes 20a and 23a is formed. This intermediate | middle laminated material 42 has the electrical power collector materials 31 and 32 in which the through-holes 20a and 23a were formed. The film material 33 is provided in one surface side of the collector material 31, and the electrode mixture layer 35 is provided in the other surface side of the collector material 31. As shown in FIG. Moreover, the film material 33 is provided in one surface side of the collector material 32, and the electrode mixture layer 36 is provided in the other surface side of the collector material 32. As shown in FIG. In this first slurry coating process, since the film material 33 and the electrode mixture layer 35 are provided in the current collector stacking unit 30, the electrode slurry passes through the through holes 20a and 23a and exits to the back surface side. Do not. Therefore, it becomes possible to form the electrode mixture layer 36 efficiently, conveying the electrical power collector laminated unit 30 in a horizontal direction.

As shown in FIG. 4, in the following step S107, the electrical power collector peeling process which peels the electrical power collector materials 31 and 32 from the electrical power collector laminated unit 30 is performed. As illustrated in FIG. 6C, in the current collector peeling step, the current collector materials 31 and 32 including the electrode mixture layers 35 and 36 are peeled from the film material 33, respectively. In addition, when the heat peeling film is used as the film material 33, since the adhesive force of the heat peeling film falls with the passage of the drying furnace 103, it is possible to peel off the collector materials 31 and 32 easily. Become.

As shown in FIG. 4, in the following step S108, the 2nd slurry coating process (2nd) which forms the 2nd electrode mixture layer 39 in the uncoated surface 37 of the peeled current collector material 31 Coating process) is performed. Similarly, in step S109, a second slurry coating step of forming the second electrode mixture layer 40 on the uncoated surface 38 of the peeled current collector material 32 is performed. In these 2nd slurry coating processes, as shown to FIG. 6D, the uncoated surface 37 of the electrical power collector materials 31 and 32 is arrange | positioned in the state arrange | positioned below. 38) is coated with an electrode slurry. The electrode mixture layers 39 and 40 are formed on the uncoated surfaces 37 and 38 of the current collector materials 31 and 32 by drying the electrode slurry. Also in this second slurry coating step, the electrode mixture layers 35 and 36 are provided in the current collector materials 31 and 32, so that the electrode slurry passes through the through holes 20a and 23a and the current collector materials 31 and 32. Do not exit to the back side. Therefore, the electrode mixture layers 39 and 40 can be efficiently formed while conveying the collector materials 31 and 32 in the horizontal direction.

As described above, since the etching treatment is performed on the plurality of current collector materials 31 and 32 simultaneously, the positive electrode current collector 20 and the negative electrode current collector 23 having the through holes 20a and 23a are formed. It is possible to lower the manufacturing cost. In addition, since the film material 33 is sandwiched between the current collector materials 31 and 32, the coated electrode slurry can be prevented from escaping from the through holes 20a and 23a. As a result, the electrode slurry can be coated while conveying the current collector materials 31 and 32 in the horizontal direction, thereby improving the productivity of the electrode and lowering the manufacturing cost. In addition, although the film material 33 is provided as a blocking layer, it is not limited to this. For example, by applying resist ink between the current collector materials 31 and 32, a resist layer as a blocking layer may be provided between the current collector materials 31 and 32.

Next, the manufacturing method of the electrode which is another embodiment of this invention is demonstrated. 8 is a flowchart illustrating a method of manufacturing the electrode, which is another embodiment of the present invention. 9-11 is a schematic diagram which shows the state of the electrode in each manufacturing process. In addition, about the member same as the member shown in FIG. 5 and FIG. 6, the same code | symbol is attached | subjected and the description is abbreviate | omitted. As the resist ink or etching solution, the same resist ink or etching solution as described above is used.

As illustrated in FIG. 8, in step S201, a current collector stacking step of forming the current collector stacking unit 50 is performed. In the current collector stacking step, as illustrated in FIG. 9A, the current collector stacking unit 50 is formed by directly stacking a pair of current collector materials 31 and 32. Subsequently, as shown in FIG. 8, in step S202, the film attachment process in which the film material 33 as a blocking layer is adhere | attached to the collector laminated unit 50 is performed. In this film attachment process, as shown to FIG. 9B, the film material 33 is adhere | attached on the whole one surface 50a of the collector laminated unit 50. As shown to FIG. In step S203, a resist printing step of forming a resist layer 51 as a protective layer on the current collector stacking unit 50 is performed. In this resist printing process, as shown in FIG. 9C, a resist layer 51 having a predetermined pattern is formed on the other surface 50b of the current collector stacking unit 50. Thus, a protective layer formation process is performed by a film attachment process and a resist printing process.

As shown in FIG. 8, in the following step S204, the etching process of forming the through-holes 20a and 23a in the collector laminated unit 50 is performed. In this etching process, as shown to FIG. 9D, an etching process is performed to the electrical power collector laminated unit 50 using the film material 33 and the resist layer 51 as a mask. As a result, a plurality of through holes 20a and 23a are formed for the respective current collector materials 31 and 32 from the other surface 50b of the current collector stacking unit 50. Subsequently, as shown in FIG. 8, in step S205, a resist removing step of removing the resist layer 51 from the current collector stacking unit 50 is performed. In this resist removal process, as shown to FIG. 9E, the resist layer 51 of the predetermined pattern provided in the other surface 50b of the collector laminated unit 50 is removed. As a result, the film materials 33 for closing the through holes 20a and 23a are provided in the current collector materials 31 and 32 in which the through holes 20a and 23a are formed.

As described above, since the etching treatment is performed on the plurality of current collector materials 31 and 32 at the same time, the production cost of the positive electrode current collector 20 or the negative electrode current collector 23 having the through holes 20a and 23a is reduced. It becomes possible to greatly reduce. In addition, by adhering the film material 33 to the current collector stacking unit 50, the current collector materials 31 and 32 are subjected to etching treatment from one surface side. Thereby, since it is not necessary to position the pattern of the resist layer 51 formed in the collector laminated unit 50 with high precision, it is lowering the manufacturing cost of the positive electrode collector 20 or the negative electrode collector 23. It becomes possible.

Subsequently, as shown in FIG. 8, in step S206, the 1st slurry coating process (1st coating process) which forms the 1st electrode mixture layer 35 in the electrode A comprised by one current collector material 31 is carried out. ) Is carried out. In this first slurry coating step, as shown in FIG. 10A, an electrode slurry is coated on the other surface (surface) 50b of the current collector stacking unit 50. Moreover, you may coat so that an electrode slurry may be filled in the through hole 20a, 23a. Then, the electrode mixture layer 35 is formed on the surface 50b of the current collector stacking unit 50 by drying the electrode slurry. Thus, in the manufacturing process of an electrode, the intermediate | middle laminated material 52 as a manufacturing object provided with the film material 33 which closes the through-holes 20a and 23a is formed. This intermediate | middle laminated material 52 is an electrical power collector material 31 and 32 in which the through-holes 20a and 23a were formed, the film material 33 provided in one surface side of the electrical power collector materials 31 and 32, and The electrode mixture layer 35 provided on the other surface side of all the materials 31 and 32 is provided.

As described above, the film material 33 is adhered to the current collector stacking unit 50 over the entire surface. Therefore, even when the electrode slurry is coated on the current collector materials 31 and 32 having the through holes 20a and 23a, the electrode slurry passes through the through holes 20a and 23a and the rear surface of the current collector stacking unit 50 is used. Do not exit to the side. Therefore, it becomes possible to convey the collector laminated unit 50 in a horizontal direction, without attaching an electrode slurry to the guide roller 104 etc. This makes it possible to set the drying furnace 103 longer than the coating method of raising the current collector material in the vertical direction. Therefore, the conveyance speed of the collector materials 31 and 32 can be raised, and the productivity of an electrode can be improved. Further, in the current collector materials 31 and 32 in which the through holes 20a and 23a are formed, the strength is lower than that of the current collector material without the through holes. For this reason, it has become difficult to raise the conveyance speed of the collector materials 31 and 32 in which the through-holes 20a and 23a were formed. On the other hand, it is possible to raise the intensity | strength by superimposing the collector materials 31 and 32 and adhering the film material 33. FIG. Thereby, the conveyance speed of the collector materials 31 and 32 can be made high, and it becomes possible to improve productivity of an electrode.

Subsequently, as shown in FIG. 8, in step S207, a current collector peeling step of peeling the current collector material 31 from the current collector stacking unit 50 is performed. As shown in FIG. 10B, in the current collector peeling process, the current collector material 31 including the electrode mixture layer 35 is formed from the current collector material 32 including the film material 33. Peel off. Subsequently, as shown in FIG. 8, in step S208, a second slurry coating step of forming the second electrode mixture layer 54 on the uncoated surface 53 of the current collector material 31 that has been peeled off (second coating step). ) Is carried out. In this second slurry coating step, as shown in FIG. 10C, the electrode slurry is disposed on the uncoated surface 53 of the current collector material 31 in a state where the electrode mixture layer 35 is disposed below. It is coated. Moreover, you may coat so that an electrode slurry may be filled in the through hole 20a, 23a. The electrode mixture layer 54 is formed on the uncoated surface 53 of the current collector material 31 by drying the electrode slurry. Also in this second slurry coating step, since the electrode mixture layer 35 is already provided in the current collector material 31, the electrode slurry passes through the through holes 20a and 23a and falls out toward the back surface side of the current collector material 31. Do not go out. Thereby, it becomes possible to form the electrode mixture layer 54 efficiently, conveying the collector material 31 in a horizontal direction.

As shown in FIG. 8, in the following step S209, the 1st slurry coating process which forms the 1st electrode mixture layer 55 is performed to the electrode B comprised by the other electrical power collector material 32. As shown in FIG. In this 1st slurry coating process, as shown to FIG. 11 (A), an electrode slurry is coated on the surface 32a of the electrical power collector material 32 in the state which has arrange | positioned the film material 33 below. . Moreover, you may coat so that an electrode slurry may be filled in the through hole 20a, 23a. The electrode mixture layer 55 is formed on the current collector material 32 by drying the electrode slurry. Also in this first slurry coating step, since the film material 33 for closing the through holes 20a and 23a is formed in the current collector material 32, the electrode slurry passes through the through holes 20a and 23a and the current collector. It does not exit to the back side of the material 32. Thereby, it is possible to form the electrode mixture layer 55 efficiently while conveying the collector material 32 in the horizontal direction.

As shown in FIG. 8, in the following step S210, the film peeling process which removes the film material 33 from the electrical power collector material 32 is implemented. In this film peeling process, as shown to FIG. 11 (B), the film material 33 remained by the electrical power collector material 32 is removed. Subsequently, as shown in FIG. 8, in step S211, a second slurry coating step of forming the second electrode mixture layer 56 on the current collector material 32 is performed. In this second slurry coating step, as shown in FIG. 11C, the electrode slurry is disposed on the uncoated surface 57 of the current collector material 32 in a state where the electrode mixture layer 55 is disposed below. It is coated. Moreover, you may coat so that an electrode slurry may be filled in the through hole 20a, 23a. The electrode mixture layer 56 is formed on the uncoated surface 57 of the current collector material 32 by drying the electrode slurry. Also in this second slurry coating step, the electrode mixture layer 55 is already provided in the current collector material 32, so that the electrode slurry passes through the through holes 20a and 23a and falls out to the rear surface side of the current collector material 32. Do not go out. Thereby, it becomes possible to form the electrode mixture layer 56 efficiently, conveying the collector material 32 in a horizontal direction.

As described above, since the etching treatment is performed on the plurality of current collector materials 31 and 32 simultaneously, the positive electrode current collector 20 and the negative electrode current collector 23 having the through holes 20a and 23a are formed. It is possible to lower the manufacturing cost. Moreover, since the film material 33 is provided in the collector laminated unit 50, it becomes possible to prevent the escape of the coated electrode slurry from the through-holes 20a and 23a. As a result, the electrode slurry can be coated while conveying the current collector materials 31 and 32 in the horizontal direction, thereby improving the productivity of the electrode and lowering the manufacturing cost.

In the above description, the film material 33 is adhered to the entirety of one surface 50a of the current collector stacking unit 50, but from the viewpoint of etching simultaneously on a plurality of current collector materials, the current collector The resist layer may be provided on the entirety of one surface 50a of the stacking unit 50. 12A to 12E are schematic diagrams showing respective manufacturing steps when forming through holes in the current collector material. In addition, about the member same as the member shown in FIG. 9, the same code | symbol is attached | subjected and the description is abbreviate | omitted. As the resist ink or etching solution, the same resist ink or etching solution as described above is used.

As shown in FIG. 12A, the current collector stacking unit 50 is formed by directly stacking a pair of current collector materials 31 and 32. In addition, as shown in FIG. 12B, the resist ink is printed on the entirety of one surface 50a of the current collector stacking unit 50. In addition, as shown in FIG. 12C, the resist ink is printed on the other surface 50b of the current collector stacking unit 50 in a predetermined pattern. As a result, a resist layer 58 is formed on one surface 50a of the current collector stacking unit 50 as a whole. On the other hand, a resist layer 51 of a predetermined pattern is formed on the other surface 50b of the current collector stacking unit 50.

Subsequently, as illustrated in FIG. 12D, the current collector stacking unit 50 is etched using the resist layers 51 and 58 as masks. As a result, a plurality of through holes 20a and 23a are formed for the respective current collector materials 31 and 32 from the other surface 50b of the current collector stacking unit 50. In addition, as shown in FIG. 12E, the overall applied resist layer 58 provided on one surface 50a of the current collector stacking unit 50 is removed. In addition, the resist layer 51 of a predetermined pattern provided on the other surface 50b of the current collector stacking unit 50 is removed. As a result, the current collector materials 31 and 32 on which the through holes 20a and 23a are formed can be obtained.

As described above, since the etching treatment is performed on the plurality of current collector materials 31 and 32 at the same time, the manufacturing cost of the positive electrode current collector 20 or the negative electrode current collector 23 in which the through holes 20a and 23a are formed is reduced. It becomes possible to greatly reduce. Moreover, by providing the resist layer 58 apply | coated entirely to the collector laminated unit 50, it is made to perform the etching process with respect to each collector material 31,32 from one surface side. Thereby, since it is not necessary to position the pattern of the resist layer 51 formed in the collector laminated unit 50 with high precision, it is lowering the manufacturing cost of the positive electrode collector 20 or the negative electrode collector 23. It becomes possible.

Next, the manufacturing method of the electrode which is another embodiment of this invention is demonstrated. It is a flowchart which shows the manufacturing method of the electrode which is another 3rd embodiment of this invention. In addition, about the process similar to the process shown in FIG. 8, the same code | symbol is attached | subjected and the description is abbreviate | omitted.

As shown in FIG. 13, in step S301, a polymerization rolling step (current collector stacking step) of forming the current collector stacking unit 50 is performed. 14 is a schematic diagram showing an example of the polymerization rolling device 110. As shown in FIG. 14, two rolls 113 and 114 for releasing the metal foil materials 111 and 112 are provided in the polymerization rolling device 110. Moreover, the pair of rolling rollers 115 which roll the metal foil materials 111 and 112 are provided in the polymerization rolling device 110. The metal foil materials 111 and 112 released from each of the rolls 113 and 114 are guided to the rolling roller 115 in an overlapped state. The current collector materials 31 and 32 are formed from the metal foil materials 111 and 112 by polymerizing and rolling the pair of metal foil materials 111 and 112 by the rolling roller 115. A current collector stacking unit 50 obtained by directly stacking 32 is formed. And the current collector materials 31 and 32 in which the through-holes 20a and 23a were formed by performing the above-mentioned resist printing process, an etching process, and a resist removal process with respect to the electrical power collector laminated unit 50 obtained by superposition | polymerization rolling. It becomes possible to obtain.

Thus, by using the polymer-rolled current collector materials 31 and 32 as they are, as the current collector stacking unit 50, the positive electrode current collector 20 and the negative electrode current collector 23 having the through holes 20a and 23a are used. It is possible to significantly reduce the manufacturing cost. That is, it becomes possible to serve as the polymerization rolling process required when manufacturing the current collector materials 31 and 32 and the current collector lamination process for forming the current collector lamination unit 50. Therefore, the number of manufacturing processes at the time of manufacturing the positive electrode collector 20 or the negative electrode collector 23 in which the through holes 20a and 23a are formed can be greatly reduced.

Hereinafter, the components of the power storage device described above will be described in detail in the following order. [A] positive electrode, [B] negative electrode, [C] positive electrode current collector and negative electrode current collector, [D] lithium electrode, [E] separator, [F] electrolyte, [G] outer container.

[A] anode

The positive electrode has a positive electrode current collector and a positive electrode mixture layer integrated therein. When the electrical storage device functions as a lithium ion capacitor, it is possible to employ a material capable of reversibly doping and dedoping lithium ions and / or anions as the positive electrode active material included in the positive electrode mixture layer. That is, it will not specifically limit, if it is a substance which can do reversibly doping / dedoping at least any one of lithium ion and anion. For example, it is possible to use activated carbon, transition metal oxides, conductive polymers, polyacene materials and the like.

For example, activated carbon is alkali activated, and it is preferable to be formed from the activated carbon particle | grains which have a specific surface area of 600 m <2> / g or more. As a raw material of activated carbon, a phenol resin, petroleum pitch, petroleum coke, coconut shell, coal type coke, etc. are used. Phenolic resin and coal type coke are suitable for the reason that a specific surface area can be raised. The alkali activator used for alkali activation treatment of these activated carbons is preferably salts or hydroxides of metal ions such as lithium, sodium and potassium. Especially, potassium hydroxide is suitable. Examples of the alkali activation method include a method of mixing a carbide and an activator and then heating the mixture in an inert gas stream. Moreover, the method of carrying out carbonization and an activating process, after heating an activating agent in the raw material of activated carbon previously, and heating it is mentioned. Moreover, the method of surface-treating with an alkali activator after reactivating carbide by gas activating methods, such as water vapor, is also mentioned. Activated carbon subjected to such alkali activation is pulverized using a known mill such as a ball mill. As a particle size of activated carbon, the thing of the wide range generally used can be used. For example, D50 is 2 micrometers or more, Preferably it is 2 micrometers-50 micrometers, Especially 2 micrometers-20 micrometers are the most preferable. Further, activated carbon having an average pore diameter of preferably 10 nm or less and a specific surface area of preferably 600 m 2 / g to 3000 m 2 / g is suitable. Especially, it is suitable that it is 800 m <2> / g or more, especially 1300 m <2> / g-2500 m <2> / g.

In addition, when the electrical storage device functions as a lithium ion battery (lithium ion battery), as a positive electrode active material included in the positive electrode mixture layer, a conductive polymer such as polyanine or a substance capable of reversibly doping and dedoping lithium ions is employed. It is possible to do For example, vanadium pentoxide (V ₂ O ₅ ) or lithium cobaltate (LiCoO ₂ ) can be used as the positive electrode active material. In addition, Li _x CoO _2, Li _x NiO _2, Li _x MnO _2, Li _x FeO _2, etc. of the Li _x M _y O _z (x, y, z are positive numbers, M is a metal, may be a metal of two or more It is also possible to use a lithium-containing metal oxide or a transition metal oxide or sulfide such as cobalt, manganese, vanadium, titanium, nickel or the like, which can be represented by the general formula. In particular, when a high voltage is required, it is preferable to use a lithium-containing oxide having a potential of 4 V or more relative to metallic lithium. For example, lithium-containing cobalt oxide, lithium-containing nickel oxide, or lithium-containing cobalt-nickel composite oxide is particularly suitable.

Cathode active materials, such as activated carbon mentioned above, are formed in powder form, a particle form, a short fiber form, etc. This positive electrode active material is mixed with a binder to form a slurry. Then, the positive electrode slurry containing the positive electrode active material is coated on the positive electrode current collector and dried to form a positive electrode mixture layer on the positive electrode current collector. As the binder to be mixed with the positive electrode active material, for example, rubber-based binders such as SBR, fluorine-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride, and thermoplastic resins such as polypropylene, polyethylene, and polyacrylates can be used. have. Moreover, you may add electroconductive material, such as acetylene black, graphite, a metal powder, suitably to a positive electrode mixture layer.

[B] cathode

The negative electrode has a negative electrode current collector and a negative electrode mixture layer integrated therein. The negative electrode active material included in the negative electrode mixture layer is not particularly limited as long as the lithium ion can be reversibly doped and dedoped. For example, it is possible to use graphite, various carbon materials, polyacene materials, tin oxide, silicon oxide, and the like. Graphite (graphite) and hard carbon (hard graphitizable carbon) are preferable as negative electrode active materials because they can achieve high capacity. In addition, polyacene-based organic semiconductors (PAS), which are heat treatment products of aromatic condensation polymers, are suitable as negative electrode active materials because they can achieve high capacity. This PAS has a polyacene skeleton structure. It is preferable that the atomic number ratio (H / C) of the hydrogen atom / carbon atom of this PAS exists in 0.05 or more and 0.50 or less. When H / C of PAS exceeds 0.50, since an aromatic polycyclic structure does not fully develop, doping and dedoping of lithium ion may not be performed smoothly, and there exists a possibility that the charging / discharging efficiency of an electrical storage device may fall. . When H / C of PAS is less than 0.05, there exists a possibility that the capacity of an electrical storage device may fall.

The above-mentioned negative electrode active material such as PAS is formed into powder, particle, short fiber, or the like. This negative electrode active material is mixed with a binder to form a slurry. Then, the slurry containing the negative electrode active material is coated on the negative electrode current collector and dried to form a negative electrode mixture layer on the negative electrode current collector. In addition, examples of the binder to be mixed with the negative electrode active material include fluorine-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride, thermoplastic resins such as polypropylene, polyethylene, and polyacrylate, and rubber binders such as styrene butadiene rubber (SBR). It is available. Among these, it is preferable to use a fluorine binder. Examples of the fluorine-based binder include polyvinylidene fluoride, vinylidene fluoride trifluoride ethylene copolymer, ethylene-4 fluoride ethylene copolymer, and propylene-4 fluoride ethylene copolymer. Moreover, you may add suitably conductive materials, such as acetylene black, graphite, a metal powder, to a negative electrode mixture layer.

[C] positive and negative current collectors

As the material of the positive electrode current collector and the negative electrode current collector, it is possible to use various materials generally proposed for batteries and capacitors. For example, aluminum, stainless steel, or the like can be used as a material of the positive electrode current collector. As the material of the negative electrode current collector, stainless steel, copper, nickel or the like can be used. In addition, the opening ratio of the through hole formed in the positive electrode current collector or the negative electrode current collector described above is not particularly limited, and is always 40% to 60%. Moreover, as long as it does not inhibit the movement of lithium ion, it does not specifically limit about the magnitude | size, number, etc. of a through hole. In addition, the shape of the through hole formed in the positive electrode current collector and the negative electrode current collector may be any shape such as a circle, an ellipse, a rectangle, a rhombus, and a slit.

[D] lithium electrode

As the material of the lithium electrode current collector, it is possible to use various materials generally proposed as current collectors of batteries and capacitors. As these materials, stainless steel, copper, nickel, etc. can be used. As the lithium electrode current collector, a through hole that penetrates the front and back surfaces such as expanded metal, punched metal, etching foil, net, foam, or the like may be used. In particular, a lithium-aluminum alloy or the like capable of releasing lithium ions may be used instead of the metal lithium foil adhered to the lithium electrode current collector.

[E] separator

As the separator, a porous body that is durable against an electrolyte solution, a positive electrode active material, a negative electrode active material, or the like, and has no electronic conductivity having communication pores can be used. Usually, the cloth, nonwoven fabric, or porous body which consists of paper (cellulose), glass fiber, polyethylene, a polypropylene, etc. is used. The thickness of the separator can be appropriately set in consideration of the holding amount of the electrolyte solution, the strength of the separator, and the like. The thickness of the separator is preferably thinner in order to reduce the internal resistance of the power storage device.

[F] electrolyte

As the electrolyte solution, it is preferable to use an aprotic organic solvent containing a lithium salt in that electrolysis does not occur even at a high voltage, and lithium ions can be stably present. As the aprotic organic solvent, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane, or the like The mixed solvent is mentioned. Examples of lithium salts include LiClO ₄ , LiAsF ₆ , LiBF ₄ , LiPF ₆ , LiN (C ₂ F ₅ SO ₂ ) ₂ , and the like. In addition, it is preferable to make electrolyte concentration in electrolyte solution into at least 0.1 mol / L or more in order to make internal resistance by electrolyte solution small. Furthermore, it is preferable to carry out in the range of 0.5 mol / L-1.5 mol / L.

In addition, an ionic liquid (ion liquid) may be used instead of the organic solvent. The combination of various cationic species and anionic species is proposed for the ionic liquid. Examples of the cationic species include NmethylNpropylpiperidinium (PP13), 1ethyl3methylimidazolium (EMI), diethylmethyl2methoxyethylammonium (DEME), and the like. Examples of the anionic species include bis (fluorosulfonyl) imide (FSI), bis (trifluoromethanesulfonyl) imide (TFSI), PF6-, and BF4-.

[G] Outer Container

As the outer container, various materials generally used for batteries can be used. For example, a metal material such as iron or aluminum may be used. Moreover, you may use film materials, such as resin. In addition, the shape of the outer container is not particularly limited. It can select suitably according to a use, such as a cylinder and a square. It is preferable to use the film type exterior container which used the laminated film of aluminum from a viewpoint of the miniaturization and weight reduction of an electrical storage device. In general, a three-layer laminate film having an adhesive layer such as a nylon film on the outside, an aluminum foil at the center, and a modified polypropylene on the inside is used.

(Embodiment 2)

The description of Embodiment 1 relates to a current collector stacking unit in which a plurality of current collector materials are stacked.

As also described in the first embodiment, one of the forms of the current collector lamination unit is a configuration in which a current collector material is laminated with a film material (blocking layer) interposed therebetween, for example. The current collector stacking unit having such a configuration can make the conveyance speed faster than when the current collector material which is perforated without conveying the film material is conveyed. For example, horizontal conveyance can be faster. That is, the current collector material is laminated on both sides of the film material with a certain amount of adhesive force, so that the strength reinforcement by the film material is achieved in conveying the laminated current collector material.

Thus, in the structure which laminated | stacked the electrical power collector material which perforated on both surfaces of the film material, the force, such as a tensile force, acts on both surfaces of a film material. Such a force such as tensile force strongly acts on the point of contact with the hole portion of the current collector material laminated on both sides of the film material. If the force acting on both surfaces of such a film material is too large than the drag force which generate | occur | produces, a film material will be damaged. For this reason, it is more preferable to disperse | distribute the force which acts on a film material rather than focusing on a pole force specific area | region.

That is, it is preferable that the position of the through-hole which opposes the hole position formed in the laminated current collector material is mutually shift | deviated. Specifically, as shown in FIG. 5 (D) and the like of the first embodiment, positions of open holes penetrating through the current collector materials 31 and 32 provided with the film material 33 therebetween, respectively. It is more preferable to shift.

In FIG. 15A, when the positions of the through-holes 20a and 23a opened in the respective current collector materials 31 and 32 provided with the film material 33 as the blocking layer therebetween coincide with each other. Is shown. That is, the film surface of the through holes 20a and 23a formed in the current collector material 32 has an opening surface α facing the film material 33 side of the through holes 20a and 23a formed in the current collector material 31. The opening face β facing the (33) side coincides with the position thereof. This opposing situation was illustrated by connecting the through-holes formed in the current collector materials 31 and 32 on both sides to the film material 33 with broken lines.

On the other hand, in FIG. 15B, the positions of the through holes 20a and 23a opened in the current collector materials 31 and 32 provided with the film material 33 as the blocking layer interposed therebetween are shifted from each other. Illustrated the case. That is, the opening surface α on the film material 33 side of the through holes 20a and 23a formed in the current collector material 31 is the film material 33 of the through holes 20a and 23a formed in the current collector material 32. The opening surface β on the) side and the position are shifted from each other.

Thus, it is the strength in a film material that the position of opening surface (alpha, beta) of the through-hole 20a, 23a formed in each collector material 31, 32 comrades is shifted firmly. It is preferable. As shown schematically in FIG. 5C of the first embodiment, the holes of the through holes 20a and 23a are formed by etching or the like in accordance with the hole arrangement of a predetermined pattern of the resist layer 34. The resist layer 34 is formed using a pattern forming means including a method of exposing and developing using a mask on which an array pattern with holes is opened.

In this manner, the planar shape of the hole formed with the resist layer 34 interposed therebetween may include various forms such as a circle, a polygon, and an irregular shape. That is, various shapes can be applied to the planar shape of the opening surface facing the film material of the through hole formed in the current collector material as described above. In addition, although a shape is mentioned later, a shape with an angle rather than a round shape may be preferable among various shapes. For example, an angled shape may be preferable from the viewpoint of preventing the omission of the electrode material filled in the through holes 20a and 23a.

For example, when the planar shape of the opening surface which faces the film material side of the through-holes 20a and 23a is a round shape, the hole pattern as shown to FIG. 16 (A) is mentioned. In such a hole pattern, for example, through holes 20a and 23a having the same opening surface shape are arranged in a zigzag shape in a longitudinal direction at a constant pitch in the longitudinal direction and in the transverse direction. In addition, in the case shown in Fig. 16A, the planar situation in the case where a part of the current collector material 31 formed in a strip shape and elongated in a predetermined width is cut.

For example, through holes 20a and 23a are formed on the current collector material 31 side in a hole pattern having the configuration shown in FIG. 16A. Although not shown, through holes 20a and 23a are formed on the current collector material 32 side with the same hole pattern. In addition, in this description, the case where a hole pattern which has an arrangement of the same hole opening surface when opening a through hole in the collector materials 31 and 32 provided in the both surfaces of the film material 33 is used is demonstrated as an example. do. However, the hole patterns used for the current collector materials 31 and 32 may be different patterns, respectively.

In addition, as mentioned above, what is the same as the pattern of the through-hole opened to the collector material may be defined as the case where the shape of an opening surface, the area of an opening surface, and an opening ratio are the same. In addition, an aperture ratio can be defined as the area ratio of the opening surface in an electrical power collector. That is, strictly, it is a ratio with respect to the area of the electrical power collector metal part of the total area of the opening surface of an electrical power collector. The current collector is produced by cutting the current collector material into pieces. The opening ratio can be measured by verifying the manufactured current collector. For simplicity, the aperture ratio may also be calculated from the ratio of the total area of the opening surface per unit area set to the current collector material.

FIG. 16B schematically shows a state of predicting the current collector material 32 side provided to face each other with the film material 33 therebetween from the current collector material 31 side. The solid circle is the opening surface α of the through holes 20a and 23a formed in the current collector material 31. The circular two-dot chain line shows the opening surface β of the through holes 20a and 23a formed in the current collector material 32. The film material 33 sandwiched in between is omitted in the drawing for ease of understanding. Hereinafter, in the figure explaining the overlapping situation of the through-hole, the film material 33 is abbreviate | omitted and shown similarly.

In FIG. 16B, the position of the opening surface α of the through holes 20a and 23a opened to the current collector material 31 is determined by the positions of the through holes 20a and 23a opened to the current collector material 32. The position of the opening surface β is shifted. In this way, in order to shift the positions of the opening surfaces α and β of the through holes 20a and 23a formed in the current collector materials 31 and 32, they are provided on the current collector material 31 and 32 surfaces. It is good to make the hole penetrate by shifting the position of the hole pattern of a resist layer.

Basically, as shown in Fig. 16B, if the opening surfaces α and β of the opposing holes are slightly displaced from each other, they are improved in strength in a strict sense, as compared with the case where they coincide with each other. I think. However, as the case where the effect of strength can be clearly recognized substantially, as shown in FIG. 17, the ratio of the area of the overlapping part (shown as an oblique part in the figure) of the opening surfaces α and β is the opening surface. What is necessary is just the predetermined value or less of the area of (alpha) (or opening surface (beta)). That is, it is preferable that the ratio (hereinafter sometimes referred to as overlap ratio) of the overlapped portion of the aperture surface α and the aperture surface β is 50% or less. Of course, the overlap rate may be 0%. The basis of 50% or less is a balance with the opening ratio of the current collector materials 31 and 32. The lower the overlap ratio, the lower the opening ratio of the current collector materials 31 and 32.

More preferably, it should just be 10% or more and 30% or less. If it is less than 10%, a problem may be considered in the opening ratios of the current collector materials 31 and 32. When it exceeds 30%, a problem may be considered in the strength of the support of the opening. In the range of 10% or more and 30%, in the present experiment, the problem considered by the intensity | strength fall of the film material stated by the previous description does not arise.

In addition, although the overlap ratio (%) was demonstrated on the premise of the case where the opening surfaces (alpha) and (beta) have the same area in the above description, in the case of a different area, the overlap ratio is represented by the ratio with respect to the opening surface of a large area. It is good to define.

In addition, when through-holes are formed in the current collector material, a step of forming a resist layer having a pattern of holes arranged on the surface of the current collector material by printing or the like and then winding again in a roll shape is assumed. In the current collector laminated unit wound in a roll shape, a tensile force or the like of different sizes acts strictly on the inside and the outside of the roll, and there is a possibility that the position shift of the resist layer occurs. Therefore, it is preferable to set the overlapping rate to any particular range rather than to set any particular value.

That is, if such a redundancy is set in a specific range, even when the resist layer is formed on the surface of the current collector material, the hole patterns of the resist layers of each other on the current collector material 31, 32 side are easily shifted. If the shifted position is set to a specific value, it takes time to set the position alignment, as to completely match the position of the opening surface. Reduction of the number of processes required for position alignment also leads to an improvement in production efficiency, which is very important in mass production. As a matter of course, the production cost can be reduced as much.

Moreover, the structure of an electrical power collector laminated unit can also be made thin by shifting the hole position which the opening surface of the through-hole of the electrical power collector material provided in both surfaces by sandwiching the film material opposes. As a structure which matches the opposing hole position, when using the film material of the same composition, for example, as shown in FIG. 18, the structure which enlarges the thickness D of a film material in order to ensure the strength can be considered. In the case shown in FIG. 18, the thickness D of the film material 33 is thick about 2 times compared with the case of the thickness d shown to FIG. 15B, for example. However, with the structure which shifted the hole position, as shown, for example in FIG. 15B, the thickness d of the film material 33 can be made thin.

The overlapping ratio of the through holes 20a and 23a is also influenced by the degree of the number of holes in the current collector materials 31 and 32. The degree of the number of holes is understood, for example, by the aperture ratio. When the holes are formed at the same pitch as the adjacent holes, when the same hole pattern having an opening ratio of more than 50% is used for the current collector materials 31 and 32, there is no overlapping rate of 0%. In other words, a configuration in which the opening surface α and the opening surface β of the hole do not overlap at all is unthinkable.

In addition, 0% of overlap ratio shows the case where aperture surface (alpha) and aperture surface (beta) do not overlap at all. Moreover, 100% of the overlap ratio has shown the case where opening surface (alpha) and opening surface (beta) correspond completely.

This overlapping rate can be confirmed, for example, by irradiating the light passing through the film sandwiched between the current collector materials of the current collector laminated unit from one current collector material side to the other current collector material side. What is necessary is just to irradiate the light from which the transmittance | permeability of an electrical power collector material and a film material differs. For example, the current collector material does not transmit, but the film material may use light having a property such as transmission. It is possible to determine the degree of transmission such as the amount of transmission, the area of transmission, and the like.

In this determination, when the holes formed in the current collector material are arranged with regularity, it can be easily verified with the above permeability per unit area. For example, in the hole pattern etc. which the planar shape of the opening surface of the through-hole formed is constant, and the pitch with the adjacent opening surface is regular, and is arrange | positioned, it overlaps with the said transmittance per unit area set suitably, etc. The rate can be calculated.

As the structure of the above description, various methods can be considered to shift the opening surface of a hole. For example, the case where the two openings of circular opening surfaces (alpha, beta) are formed in the electrical power collector materials 31 and 32 is taken as an example. As shown to FIG. 19A, as a direction which shifts the position of opening surface (alpha), (beta), basically, the x- and y-axis direction which mutually goes mutually can be assumed, for example. FIG. 19B illustrates a case where the shift in the x-axis direction occurs. In FIG. 19B, it partially overlaps and shifts the opening surfaces α and β. In the case shown in FIG. 19C, the case where the overlap is not generated in the x axis direction so as not to occur, that is, the overlap ratio is 0%, is illustrated.

In addition, as shown to FIG. 20 (A), it can also assume that it shifts so that a part may overlap in the y-axis direction. The case shown in FIG. 20B is a case where the overlap ratio is shifted by 0% in the y-axis direction. Further, as shown in FIG. 20C, the opening surfaces α and β can be shifted in both directions of the x-axis and the y-axis. In addition, although not shown, when the pitch of the adjacent opening surface (alpha) is smaller than the diameter of the opening surface (alpha), even if it shifts to the x-axis or the y-axis direction, the opening surface (beta) is formed in both of the adjacent opening surfaces (alpha). You can think of duplicate cases.

In FIG. 21A, the arrangement pattern of the opening surface α of the drilled through holes 20a and 23a in the current collector material 31 is different from that in FIG. 16A. As such a hole pattern, circular opening surface (alpha) is aligned by the same pitch in a longitudinal direction and a lateral direction. In addition, as shown in FIG. 16A, FIG. 21A illustrates a situation in which a part of the perforated current collector material 31 formed in a long shape is cut. Although not shown, through-holes 20a and 23a are formed in the current collector material 32 in the same hole pattern.

FIG. 21B shows a case where both of the current collector materials 31 and 32 having through holes having such a configuration are arranged to face each other with the film material 33 interposed therebetween. In FIG. 21B, the current collector material 32 side is predicted from the current collector material 31 side. As in the description of FIG. 16B, the solid line is the opening surface α, the two-dot chain line is the opening surface β, and the illustration of the film material 33 sandwiched therebetween is omitted.

As shown in FIG. 21B, the position of the opening surface α of the drilled through holes 20a and 23a in the current collector material 31 is the through hole 20a, which is open to the current collector material 32. The position is shifted | deviated from the opening surface (beta) of 23a) in the x-axis direction. For this reason, as mentioned above, the both surfaces of the film material 33 interposed between them are disperse | distributed without a force, such as a tensile force, acting at the same point. Compared with the case where the position of the opening surface of the hole to correspond is matched, the intensity | strength of a film material is ensured more strongly. FIG. 22A illustrates a case where the shift in the y-axis direction occurs. FIG. 22B illustrates a case where the shift in the x-axis direction and the y-axis direction occurs. In FIG. 23, the case where the overlap ratio is 0% is shown.

In the above description, similarly to the first embodiment, the through holes 20a and 23a illustrate the case where the cross section is formed in a straight line. That is, as shown to (A) and (B) of FIG. 15, opening surface (alpha), (beta) is provided in the film material 33 side of the electrical power collector material 31, 32 in contact with it. Opening surfaces α1 and β1 are provided on the surfaces 30a and 30b sides of the current collector materials 31 and 32. Such opening surfaces α and α1 and opening surfaces β1 and β have the same size. In the case where the through holes 20a and 23a are actually formed, a process is performed in which holes such as etching are opened in the current collector material so as to be linear by providing anisotropy in the through direction.

However, when through-holes 20a and 23a are formed using a process of opening a hole such as etching without being aware of anisotropy, the shape of through-holes 20a and 23a becomes a tapered shape. In other words, the opening surfaces α1 and β1 on the surfaces 30a and 30b side of the current collector materials 31 and 32 are larger than the opening surfaces α and β in contact with the film material 33.

In the case shown in FIG. 24A, the positions of the opening surfaces α and β of the through holes 20a and 23a formed in the current collector materials 31 and 32 facing each other with the film material 33 interposed therebetween. Is a match. In the case shown in FIG. 24B, the positions of the opening surfaces α and β of the through holes 20a and 23a formed in the current collector materials 31 and 32 facing each other with the film material 33 interposed therebetween. It is the case that is shifted. Even in such a non-linear through-hole shape, the opening surfaces α and β on the side facing the film material 33 are as shown in Figs. 16B, 21B, 22, 23 and the like. It is preferable that the hole pattern is shifted.

In this case, the strength of the current collector stacking unit 30 is strengthened as a whole as compared with the case where there is a mismatch. As a result, horizontal conveyance can be made faster than when the opening surfaces (alpha) and (beta) match. Moreover, the thickness of the film material 33 as a blocking layer interposed between them can also be made thin.

In order to shift the positions of the opening faces of the through holes formed in the plurality of current collector materials laminated with the film materials (blocking layers) explained above, the etching resist layer provided on the surface of each current collector material The hole pattern may be shifted and set. In this way, the opposing positions of the opening surfaces of the through holes formed in accordance with the pattern of the resist layer are formed to be shifted including the overlap rate 0.

In other words, by consciously shifting the resist patterns provided on both current collector materials 31 and 32, the opening surface α and the opening surface β of the holes opened by etching are shifted. The degree of misalignment may be set so as to be 50% or less, including 0% of the overlapping ratio of the opening surfaces α and β, for example. Furthermore, it is good to set so that it may become 10% or more and 30% or less of redundancy.

As described above, it is preferable from the viewpoint of strength that the opening faces of the through holes of the current collector material are provided to face each other with a blocking layer such as a film interposed therebetween, and the positions of the opening faces of the current collectors shifting from each other. That is, as shown in the explanatory drawing of the etching process of FIG. 5 (C) of the said Embodiment 1, the position of the hole of the electrical power collector material 31, 32 in both sides of the film material 33 is used as an opposing position. It is preferable to shift.

The opening of the hole in the current collector material at the position opposite to each other with the film material is determined by the pattern for opening the hole of the resist layer when, for example, etching is used. The opening surface of the hole formed in this way is very small. For this reason, it was difficult to match an opening surface, it took time, and production cost was expensive.

This has been solved by a very simple method of shifting the positions of the opposing opening faces within, for example, a certain range, and at the same time, the strength of the current collector stacking unit is also improved. Regarding the positional alignment, since the trouble of exact positional alignment is eliminated and an approximate positional alignment is possible, the production cost of an electrical power collector material and an electrical power collector can be reduced. In the end, the production cost of the electrode using the current collector can be reduced, and the production cost of the battery, such as a battery and a capacitor, using the electrode can be reduced.

In addition, in terms of the strength of the current collector stacking unit, when the pore positions of the opposing opening surfaces coincide with each other, when the etching liquid is cleaned or the like, both parts of the film material sandwiched by the opening surfaces α and β are torn off. It becomes easy to lose. Or a film material is easy to be damaged by the peeling process of a resist layer, the coating process of an electrode material, the peeling process of each surface of the film material which is a blocking layer, or the peeling process of both surfaces, etc. Even if it is not damaged, obstacles such as wrinkles occur.

However, by adopting such a configuration that the hole positions of the opposing opening surfaces are shifted, it is possible to prevent such breakage of the film material, generation of wrinkles, and the like. For this reason, it leads to the improvement of the intensity | strength as the whole collector laminated unit. As a result, the speed of horizontal conveyance in the process after an etching process can be set faster than the case where a hole position is not shifted.

In the above description, the case where the hole pattern of the opening surface of the through-hole to the collector material provided through the film material was the same pattern was demonstrated as an example. However, the hole pattern opening to the collector material laminated | stacked on each film material may be made different. When producing on the premise of using in the electrode used by the same capacitor | capacitor, the same hole pattern is used. However, in order to produce an electrical power collector with a different aperture ratio, you may laminate | stack different current collector materials, and may form an electrical power collector laminated unit at all.

In particular, when the aperture ratio of the hole pattern is different, even when the aperture ratio of one current collector material exceeds 50%, the current collector material having an aperture ratio of less than 50% can be used on the other side. In that case, it is also possible to set the overlap rate to zero or close to zero.

The configuration described above can be described as, for example, the following 占 로서는 as the technical range. That is, the technical range 1 is, for example, a method for producing a current collector that is made by separating the current collector material into pieces, wherein the opening surfaces of the through holes in each of the current collector materials provided opposite to each other are shifted. It can be described as a manufacturing method. As technical range 2, for example, in the manufacturing method of the electrical power collector described in technical range 1, shifting the opening surface of the said through hole can be described as shifting so that opposing opening surfaces may not overlap. As the technical range 3, for example, in the manufacturing method of the electrical power collector described in technical range 1, shifting the opening surface of the said through hole can be described as shifting so that the opposing opening surface may partially overlap. As technical range 4, for example, in the manufacturing method of the electrical power collector described in technical range 3, shifting so that the said opening surface may partially overlap may shift so that opening surfaces may overlap in the range of 10% or more and 30% or less of overlap rates. It can be described as characterized in that. As the technical range 5, in the manufacturing method of the electrical power collector as described in any one of technical ranges 1-4, the through-holes which have the same shape of an opening surface, and the arrangement | positioning of the hole of an opening surface in the said collector material provided opposingly, It can be described that it is characterized by the position of an opening surface shifting | deviating. As the technical range 6, it can be described, for example, in the manufacturing method of the electrical power collector as described in any one of technical ranges 1-4, the through-hole which differs in aperture ratio is formed in the said electrical power collector material provided in opposition. have. As technical range 7, for example, in the manufacturing method of the electrical power collector as described in any one of technical ranges 1-6, it is provided so that the said electrical power collector material may be opposed, and is interposed between blocking layers, such as a film material, in between. It can be described that there is a feature. As technical range 8, it is an electrode which has an electrical power collector with a through hole, for example, The said electrical power collector is an electrical power collector manufactured by the manufacturing method of the electrical power collector as described in any one of said technical ranges 1-7. It can be described. As technical range 9, it is an electrical storage device which has an electrode provided with an electrical power collector, for example, The said electrical power collector is an electrical power collector manufactured by the manufacturing method of the electrical power collector of any one of said technical ranges 1-7, It is characterized by the above-mentioned. It can be described as.

(Embodiment 3)

In the current collector stacking units described in the first and second embodiments, holes to penetrate through the plurality of current collector materials laminated with the blocking layer interposed therebetween were opened. In this through hole, as described in the first embodiment, an electrode slurry is coated, and then dried to form an electrode mixture layer. In the formation of such an electrode mixture layer, in some cases, the electrode mixture layer is filled in the through hole. 6, 10, and 11 of the first embodiment exemplify a configuration in which the electrode slurry is not filled in the through hole, but may be filled, for example, as shown in FIGS. 25, 26, and 27. The electrode mixture layer formed by drying the filled electrode slurry is attached so as not to be omitted by the film material as the blocking layer. However, after the electrode mixture layer is formed, as described in the first embodiment, the film material as the blocking layer is peeled off.

That is, the film material is peeled off from the current collector material laminated on the film material. At the time of such peeling, the filled electrode mixture layer may fall off. Dropping of the electrode mixture layer in the through-holes formed in the current collector material is separate as long as it occurs in all the through-holes, but usually occurs in some through-holes. From the electrical power collector material of such a structure, the electrical power collector which isolate | separates and manufactures by cutting is not uniform in the ion permeability of a through hole. The ion permeability of the through hole is different in the partial portion of the current collector.

For this reason, when assembling as an electrode laminated unit using such an electrical power collector, a remarkable difference arises in the passability of the ion, such as lithium ion which passes through a through hole. As a result, for example, the uniformity of ion doping within a predetermined time may be impaired. Alternatively, variations in the doping amount of ions at a predetermined time may occur.

Then, in this embodiment, when peeling off the film material as a blocking layer, the fall prevention prevention of the electrode mixture layer filled in the through hole was considered. As a fall prevention measure, various measures are conceivable. For example, it is possible to change the hole shape of the through hole to an appropriate shape in which the electrode mixture layer does not drop off. As the hole shape, for example, a change in the cross-sectional hole shape along the penetration direction can be considered. Or it can also think as a planar hole shape of the opening surface side facing a film material.

Until now, the through-holes, for example, in wet etching and the like, were careful to make the hole cross-sectional shape as straight as possible. That is, various measures, such as the composition of etching liquid and the mask countermeasure at the time of pattern formation of a resist layer, were implemented. Therefore, the production cost in the case of forming the through hole in the current collector material has increased.

As described in the first embodiment, in the configuration of the current collector stacking unit, the blocking layer is peeled off after the electrode mixture layer is filled in the through hole. For example, as shown also in step S107 of FIG. 4 of FIG. 1, FIG. 6 (C), etc. of the said Embodiment 1, the blocking layer, such as a film material, is peeled. In such peeling, the obstacle which the electrode mixture layer filled in the through-hole fell out has generate | occur | produced.

28 (A) and (B), the dropping of the electrode mixture layer after peeling off the film material as a blocking layer was shown. For example, as illustrated in FIG. 28A, the current collector material 31 is formed with straight through holes 20a and 23a having a straight cross-sectional shape in the penetrating direction. The electrode mixture layer 35 is filled in these through holes 20a and 23a. However, as shown in FIG. 28A, the filled electrode mixture layer 35 is easily detached from the through holes 20a and 23a.

The electrode mixture layer part 35a (35) filled in the through-holes 20a and 23a falling off is easy to fall off because the inner wall surfaces of the through-holes 20a and 23a are formed in a straight line toward the through-direction. . This is because the dropping-side opening surface θ from which the filled electrode mixture layer part 35a is missing is formed in the same manner as the filling-side opening surface θ1 cut parallel to the dropping-side opening surface θ. In addition, the side surface of the dropping-off opening surface θ and the filling-side opening surface θ1 is linearly connected. That is, it was thought that such a dropout is because there is no catching part which prevents the electrode mixture layer part 35a from falling out inside the penetration direction.

In addition, the dropping-side opening surface (theta) is a through hole formed in the electrical power collector material laminated | stacked on the film material, and shall mean the opening surface of the through hole facing the film material as a blocking layer. In other words, such a dropping-side opening surface θ may be referred to as an opening surface formed at the end of the through hole on the other end side in the through direction of the through hole from the opening surface on the coating side of the electrode slurry. In addition, the filling side opening surface (theta) 1 is an opening surface opened to the surface side in which the electrode slurry of an electrical power collector material is coated. From this filling side opening surface θ1, the electrode slurry is coated to fill the inside of the through hole.

On the other hand, also in the case shown in FIG. 28 (B), as in FIG. 28A, the dropping of the electrode mixture layer part 35a is very easy. In the structure shown in FIG. 28B, the dropping-off opening surface θ is largely opened compared with the filling-side opening surface θ1. Furthermore, the side surface which connects the dropping-side opening surface (theta) and the filling side opening surface (theta) 1 is also formed with the linear taper. The inside of the through hole is a configuration in which the electrode mixture layer portion 35a is easy to drop out very easily.

Therefore, the inventors of the present invention considered that it is sufficient to form some locking portion for preventing the electrode mixture layer portion 35a from falling off inside the through hole along the through direction. One configuration of the locking portion is to provide irregularities in the inner side surface portion of the through hole. As such an unevenness | corrugation, what is necessary is just to roughen the roughness of a through-hole inner surface in opening a through-hole by etching, for example. For example, it can cope by selecting an appropriate etching liquid, an etching rate, and the like. It can be set as a rough surface without forming the surface side of the side surface smoothly as much as possible. The rough through-hole inner side functions as a locking portion of the electrode mixture layer, and serves as a fall prevention means.

Alternatively, as shown in FIG. 29A, in the through holes 20a and 23a, the non-dropout side opening surface θ2 different from the dropout side opening surface θ and the dropout side opening surface θ is different. To change the size of the. That is, the cross-sectional shape of the non-falling side opening surface (theta) 2 cut into the surface parallel to the dropping-side opening surface (theta) at arbitrary positions of a penetration direction is made larger than the dropping-side opening surface (theta). When the through holes 20a and 23a are formed in such a structure, as shown in FIG. 29B, the electrode mixture layer part 35a in the through holes does not fall off. The electrode mixture layer part 35a is caught by the peripheral through-hole inner surface γ at the non-dropout side opening surface θ2 and can be prevented from falling off.

In addition, the through holes 20a and 23a are formed in the current collector material 31 laminated on the film material 33 as the blocking layer. Although not shown in the drawing, the film material 33 is provided with a total current material 32 facing the current collector material 31. Similarly, through holes 20a and 23a are formed in the current collector material 32.

As a cross-sectional shape effective for such fall prevention, there is also a cross-sectional structure of the through holes 20a and 23b as shown in FIG. 29C. In the case shown in FIG. 29C, the straight side surface and the side surface of which the end taper is formed along the penetration direction. The non-falling-side opening surface θ2 where the straight side surface and the tapered side cross each other is larger than the dropping-side opening surface θ. For this reason, the electrode mixture layer part 35a is caught by the through-hole inner surface, and fallout is prevented. The through holes 20a and 23a of such a cross-sectional structure can be manufactured, for example by a some etching process.

The straight portions of the through holes 20a and 23a in FIG. 29C are performed by anisotropic etching treatment for forming the straight through holes 20a and 23a as before. Thereafter, the tapered portion is subjected to an isotropic etching process. In this way, through holes 20a and 23a shown in FIG. 29C can be formed by etching in multiple stages.

On the other hand, the point where the electrode mixture layer part 35a hangs can be formed in the through-holes 20a and 23a without performing a some etching process. For example, the etching process may be performed without using any of the means for straightening currently performed. In this case, since the longer time to contact with etching liquid is etched more, the cross-sectional hole shape with a taper as shown in FIG. 30 (A) is naturally formed. The through holes 20a and 23a having such a shape are formed in the current collector material 31 laminated on the film material 33 as a blocking layer.

In the film material 33 in which the collector material 31 of such a structure is provided, as shown to FIG. 30 (A), the collector material 32 is provided and the collector laminated unit 30 is comprised. . In the current collector material 32, through holes 20a and 23a having a tapered shape similar to the current collector material 31 are formed. In addition, as described in the second embodiment, the through holes 20a and 23a facing each other with the film material 33 formed on the current collector materials 31 and 32 interposed therebetween. Is shown. The position of the opening surface of the through-holes 20a and 23a does not have to shift, unless the intensity | strength of the collector laminated unit is aimed at.

In FIG. 30B, only the current collector material 31 side laminated on the film material 33 as the blocking layer is shown, and the current collector material 32 side is not shown. As described above, when the current collector material 31 is etched without any means intended to be straight, isotropic etching is performed. In such etching, the dropping-side opening surface θ facing the film material 33 is formed smaller than the filling-side opening surface θ1. With such a hole structure, the side surface around it is formed in the cross-sectional shape connected by the linear taper from the drop-off opening surface (theta) to the opening surface of the filling side opening surface (theta) 1. In the through holes 20a and 23a thus formed, the electrode slurry is coated and filled, and then dried to fill the electrode mixture layer part 35a.

In this way, the electrode mixture layer portion 35a filled in the through holes 20a and 23a is peeled off after that, as shown in FIG. 30C. However, the electrode mixture layer part 35a is caught by the side surface part of the through-hole inner surface (gamma) of through-holes 20a and 23a, and is not missing from the dropping-side opening surface (theta) side. Even if the film material 33 is peeled off, although it is somewhat stretched to the film material 33 side, the film material 33 is prevented from being dropped to the dropping-side opening surface θ side. That is, even if the peripheral side surface is formed in a straight line, the dropping-opening surface θ is the smallest inside the through hole, so that the electrode mixture layer portion 35a filled in the through holes 20a and 23a is caught by the side surface. Dropping is prevented. That is, in such a structure, the side surface formed with the taper toward the fallout side opening surface (theta) acts as a locking means, and is an effective fall prevention means.

Such a fall prevention means can also be called a means which forms the penetrating direction by the taper which taper | tip tapers toward the film material 33 side. Alternatively, the tapered taper may be provided from the filling side opening surface θ1 which is the filling in the through hole of the electrode slurry to be coated toward the other opening surface of the dropping opening surface θ. have. Further, the tapered taper may be provided around the entire inner surface of the through hole or on a part of the peripheral surface. Furthermore, you may provide in the whole direction of a penetration direction, or a partial direction.

Thus, as shown to FIG. 30D, even after peeling off the film material 33 completely, the electrode mixture layer part 35a is affixed in the through hole 20a, 23a. That is, no dropping of the electrode mixture layer part 35a can be seen. For this reason, in the electrical power collector manufactured by the individualization of the electrical power collector material in which the hole which penetrates this structure is formed, the ion passage characteristic through the hole is maintained uniformly. Therefore, even when the electrode is configured using such a current collector, the doping function of the electrode is maintained uniformly.

In addition, the above description was made on the premise that the some electrical power collector material demonstrated in the said Embodiment 1 was laminated | stacked across the film material as a blocking layer. However, it is also applicable to the structure in which a single collector material is laminated on a film material or the like.

The structure described above can be described as follows, for example as a technical range. That is, as the technical range 1, it can be described that it is a current collector in which the through hole used for the electrode was formed, for example, The through hole is provided with the fall prevention means of the electrode mixture layer filled in the inner surface of the said through hole. have. As the technical range 2, for example, in the current collector described in the technical range 1, the drop-off preventing means cuts the opening surface of the through hole end toward the penetration direction from the coating side of the electrode slurry into a surface parallel to the opening surface. It can be described that it is characterized by being smaller than the other opening surface in one said through hole. As the technical range 3, for example, in the current collector described in the technical range 1, the fall prevention means is an end provided from an opening surface on the coating side of the electrode slurry of the through hole toward the opening surface of the other end of the through hole. It can be described that it is characterized by the tapered taper shape. As the technical range 4, for example, in the current collector described in any one of the technical ranges 1 to 3, the current collector may be described as being made from a laminated current collector material in which the through holes are formed. In the technical range 5, for example, a method of manufacturing a current collector having a through hole used for an electrode, wherein the through hole separates the current collector material provided with a fall prevention means of the electrode mixture layer filled in the inner surface of the through hole. It can be described as characterized. As the technical range 6, for example, in the manufacturing method of the electrical power collector described in the technical range 5, the said fall prevention means is made to parallel the opening surface of the through-hole end from the coating side of an electrode slurry toward a penetration direction. It can be described that it is made smaller than the other opening surface in the said through hole cut into the surface. As the technical range 7, for example, in the current collector described in the technical range 5, the fall prevention means is provided from the opening surface on the side of the electrode slurry of the through hole toward the opening surface of the other end of the through hole. It can be described that it is characterized by providing this taper taper. As the technical range 8, in the manufacturing method of the electrical power collector of any one of technical ranges 5-7, the said electrical power collector material is the said through-hole formed in the state in which the said some electrical power collector material was laminated | stacked. It can be described as characterized. As technical range 9, it is an electrode using the electrical power collector with a through hole, for example, The electrical power collector of any one of said technical ranges 1-4, or the manufacturing method of the electrical power collector of any one of said technical ranges 5-8. It can be described that it is characterized by using the electrical power collector manufactured by. As technical range 10, an electrical storage device which has an electrode, for example, The said electrode is the electrical power collector of any one of said technical ranges 1-4, or the manufacturing method of the electrical power collector of any one of said technical ranges 5-8. It can be described that it is characterized by using the electrical power collector manufactured by. In the technical range 11, for example, the electrode mixture layer prevents the dropping of the electrode mixture layer from the through hole formed in the current collector of the electrode mixture layer and prevents the electrode mixture layer filled in the through hole from falling off on the inner surface of the through hole. It can be described that it is characterized by providing the engaging part of the layer. As the technical range 12, for example, in the fall prevention structure from the through-hole of the electrode mixture layer described in the technical range 11, the said latching | locking part is larger than the opening surface of the through-hole end toward the penetrating direction from the coating side of an electrode slurry. It can be described that it is another opening surface in the said through hole cut into the surface parallel to spherical surface. As the technical range 13, in the fall prevention structure from the through-hole of the electrode mixture layer described, for example, in the technical range 11, the said latched part is a part of the other end of the said through-hole from the opening surface of the electrode slurry of the said through-hole. It can be described that the end provided toward the opening surface is a tapered taper.

(Embodiment 4)

In this embodiment, the planar shape which is an opening surface of a through hole is demonstrated. As a fall prevention means, when the planar shape of the opening surface of a through-hole was also considered important, ie, when peeling off a barrier layer, such as a film material, it can hardly peel off vertically with respect to a collector material surface. . It is assumed that peeling process is performed in the state which made it have some orientation. For example, in the case of peeling a film material from one end of a long direction with respect to a long collector material, a long direction can be prescribed | regulated as a peeling direction. In such a case, it is preferable that the planar shape of the opening face facing the film material side of the through hole formed in the current collector material is a shape in consideration of the peeling direction. A planar shape having anisotropy will be preferable to a planar shape having isotropy around 360 degrees.

For example, it can be considered that the shape is different in the peeling direction and in the direction orthogonal to this direction. That is, unlike squares, circles, regular polygons, etc., it is thought that shapes, such as a rectangle and an ellipse, are preferable. When giving priority to what is easy to peel, it is more preferable that the length of a peeling direction is shorter than the width direction orthogonal to it. On the contrary, when the electrode mixture layer in a through-hole does not fall easily, it is more preferable that the length of a peeling direction is a shape longer than the width direction orthogonal to it. That is, it is thought that what is necessary is just to set it as planar shape from which the length and breadth differ, and to adjust the longitudinal direction to the conveyance direction or peeling direction of an electrical power collector material. In some cases, it may be considered to arrange in a direction in which the longitudinal and horizontal longitudinal directions intersect with respect to the peeling direction.

Moreover, it is thought that the shape with each part rather than a round shape is easy to catch the electrode mixture layer filled in the through hole, and does not fall easily. It is more preferable that such an angle part is more acute in order to prevent the electrode mixture layer from falling off. For example, it is considered that an equilateral triangle is more effective in preventing falling out of a regular polygon and a regular polygon than a square. A better shape can be obtained by adding the concept of the length of the aspect ratio to the ranking of the shape. That is, the shape having high symmetry such as regular polygon, square, and equilateral triangle may be modified into a shape having low symmetry. For example, it is thought that the effect can be further obtained by deforming to an ellipse, a rectangle, an isosceles triangle, or the like.

This invention is not limited to the said embodiment, Of course, various changes are possible in the range which does not deviate from the summary. For example, the electrode obtained by the manufacturing method of the present invention described in the first embodiment can be applied not only to lithium ion batteries and lithium ion capacitors, but also to various types of batteries and capacitors.

In addition, in the case shown in FIG. 5 (A) and FIG. 9 (A), although it forms with the electrical power collector laminated units 30 and 50 using the two electrical power collector materials 31 and 32, three sheets are used. The current collector materials may be laminated to form a current collector laminated unit. For example, a new current collector material may be laminated on the surface of the current collector stacking unit 30 shown in FIG. 5A. Further, a new current collector material may be laminated on the surface of the current collector stacking unit 50 shown in FIG. 9A.

In addition, in the above description, although the resist removal process which removes the resist layers 34, 51, and 58 is provided, the resist layers 34, 51, and 58 have electroconductivity, and do not affect an active material, electrolyte solution, etc. If not, it is also possible to omit the resist removal process.

Claims (17)

As a manufacturing method of an electrode including a perforated current collector, A current collector stacking step of stacking a plurality of current collector materials to form a current collector stacking unit, A protective layer forming step of forming a protective layer having a predetermined pattern on a surface of the current collector stacking unit, An etching process of subjecting the current collector stacking unit in which the protective layer is formed to form a through hole in each of the current collector material; A first coating step of coating an electrode slurry on a surface of the current collector stacking unit in which the through hole is formed; A current collector peeling step of peeling the current collector material coated with the electrode slurry from the current collector stacking unit; 2nd coating process of coating an electrode slurry on the uncoated surface of the said collector material isolate | separated from the said collector laminated unit Method for producing an electrode comprising a. The method of claim 1, In the current collector stacking process, a blocking layer is interposed between the plurality of current collector materials, In the protective layer forming step, the protective layer of a predetermined pattern is formed on both of one side and the other side of the current collector stacking unit, In the etching step, the through hole is formed in each of the current collector material from both of one side and the other side of the current collector stacking unit. The method of claim 1, In the current collector stacking process, the plurality of current collector materials are directly laminated In the protective layer forming process, a blocking layer is formed on the entire surface of one side of the current collector stacking unit, while the protective layer of a predetermined pattern is formed on the other side of the current collector stacking unit, In the etching step, the through hole is formed in each of the current collector material from the other surface of the current collector stacking unit. The method according to any one of claims 1 to 3, Through-holes formed in each of the plurality of stacked current collector materials are provided to face each other, The opening surface of the through-holes which opposely provided mutually shifted, The manufacturing method of the electrode characterized by the above-mentioned. The electrode according to any one of claims 1 to 3, wherein the through-holes formed in each of the plurality of laminated current collector materials are provided with an anti-falling means of the electrode mixture layer on the inner surface of the through-holes. Manufacturing method. The said fall prevention means makes the opening surface of the through-hole end from the coating side of an electrode slurry toward a penetrating direction smaller than the other opening surface in the said through-hole cut into the surface parallel to this opening surface. The manufacturing method of an electrode made into. 6. The electrode production apparatus according to claim 5, wherein the dropout preventing means has a tapered shape in which an end provided toward the opening surface of the other end of the through hole is tapered from the opening surface of the electrode slurry of the through hole. Way. An electrical storage device in which an electrode including a perforated current collector is embedded, The said electrode is manufactured using the manufacturing method of the electrode in any one of Claims 1-3, The electrical storage device characterized by the above-mentioned. The power storage device according to claim 8, wherein said power storage device is a lithium ion capacitor. The power storage device according to claim 8, wherein said power storage device is a lithium ion battery. As an intermediate | middle laminated material as a thing under manufacture in the manufacturing process of an electrode, A current collector material comprising a plurality of through holes, A blocking layer provided on one side of the current collector material and closing the through hole; Electrode mixture layer provided on the other side of the current collector material Interlayer laminated material comprising a. 12. The intermediate laminate according to claim 11, wherein the current collector material is laminated on both sides of the blocking layer. 12. The intermediate laminate according to claim 11, wherein the current collector material is laminated on one side of the blocking layer. The collector of claim 11 or 12, wherein a plurality of the current collector materials are provided to face each other with the blocking layer interposed therebetween, The intermediate | middle laminated material characterized by the opening surface which faces the said blocking layer of the through-holes formed in each of the said collector material provided so as to oppose. The intermediate | middle laminated material of any one of Claims 11-13 in which the through-hole is provided in the inner surface with the fall prevention means of the electrode mixture layer. The intermediate | middle laminated material of Claim 15 in which the said fall prevention means makes the opening surface which faces the said blocking layer side of the said through hole smaller than the other opening surface cut | disconnected by the surface parallel to the said opening surface. The intermediate | middle laminated material of Claim 15 whose said fall prevention means is a tapered taper which the edge provided in the said through-hole toward the said blocking layer is tapered.