JP6008389B2 - Electronic component and electronic device - Google Patents

Description

  The present invention relates to an electronic component and an electronic device, for example, an electrochemical cell such as an electric double layer capacitor, an ion capacitor, or a nonaqueous electrolyte battery.

A capacitor such as an electric double layer capacitor or an ion capacitor is a device that stores electricity by polarizing ions in an electrolyte and supplies electric power by discharging the ions.
Due to this storage / discharge function, the capacitor is used, for example, as a clock function of an electronic device, a backup power source such as a semiconductor memory, or a standby power source of an electronic device such as a microcomputer or IC memory.
In particular, an electric double layer capacitor and an ion capacitor that can be surface-mounted can be reduced in size and thickness, and thus are suitable for a thin portable terminal.
In order to meet such a demand for downsizing and thinning, in Patent Document 1 below, as described below, a polarizing electrode and an electrolyte are housed in a container having a recess, and the opening is sealed with a sealing plate. Stopped electric double layer capacitors have been proposed.

FIG. 13 is a side sectional view of a conventional electric double layer capacitor 100.
A metal layer 111 is provided on the bottom surface of the ceramic concave container 102 in which the recess 113 is formed, and the positive electrode 106 is joined to the upper surface of the metal layer 111. The metal layer 111 penetrates the concave container 102 and is electrically connected to the positive electrode terminal 112 on the bottom surface of the concave container 102, so that the positive electrode 106 is electrically connected to the positive electrode terminal 112 through the metal layer 111. Connected to.
Further, the sealing plate 103 is bonded to the opening of the recess 113 by the metal bonding metal layer 108 to seal the recess 113.
A metal layer 115 that functions as a current collector is formed on the lower surface of the sealing plate 103, and the negative electrode 105 is bonded to the surface of the metal layer 115.
A metal layer 109 is formed on a side surface of the concave container 102 to connect the bonding metal layer 108 and the negative electrode terminal 110 on the bottom surface of the concave container 102.
The negative electrode 105 is electrically connected to the negative electrode terminal 110 through the metal layer 115, the bonding metal layer 108, and the metal layer 109.

A separator 107 that prevents these short circuits is provided between the negative electrode 105 and the positive electrode 106, and the negative electrode 105, the positive electrode 106, and the separator 107 are impregnated with an electrolyte.
The electric double layer capacitor 100 stores electricity when a voltage is applied to the negative electrode terminal 110 and the positive electrode terminal 112, and discharges the stored electric charge to supply power to the maintenance of a clock function, a memory, or the like.

In such an electric double layer capacitor 100, the electrolyte impregnated in the negative electrode 105 and the positive electrode 106 is always in contact with the metal layer 111 formed in the concave container 102 and the metal layer 115 formed in the sealing plate 103. It is in a state of being.
For this reason, there is a possibility that the performance of the electric double layer capacitor 1 is deteriorated by being influenced by the electrolyte in which the metal layers 111 and 115 are always in contact.

In order to eliminate the influence of such constant contact of the electrolyte, it has been necessary to use and process a specific material.
For example, as the metal layer 111 of the recess 113, a tungsten layer as a base is formed, and an aluminum layer is formed thereon.
This is due to the following reason. That is, since the metal layer 111 is used as a current collector, it is necessary to form the metal layer 111 with a material that does not dissolve in the electrolyte even when a voltage is applied due to repeated charge and discharge. In the case of the positive electrode current collector, such a substance is aluminum, but aluminum cannot withstand the firing temperature of the concave container 102 (preferably 1000 [° C.] or higher).
Therefore, a base is made of tungsten that can withstand high temperatures, and after firing the concave container 102, an aluminum layer is formed on the base of tungsten.
However, in order to form the aluminum thin film on the bottom surface of the recess 113, it is necessary to use a dry process such as vacuum vapor deposition, and there is a problem that the cost increases.

Meanwhile, in order to solve the above problem, in Patent Document 2 described techniques, on the metal layer formed on the inner bottom portion of the hollow container (tungsten), and heated solidified conductive paste to the conductive material of carbon formation By covering with the current collector, the electrolyte and the metal layer are prevented from coming into direct contact.
However, in the technique described in Patent Document 2, an organic solvent may be added for the purpose of lowering the viscosity of the conductive paste. When the solvent is vaporized, bubbles are formed, and small communication holes (holes) having a diameter of about several μm. May form. In addition, the above-described small-diameter communication holes may also be formed by gas components in the atmosphere entrained during application of the conductive paste.
Thus, even when the metal (tungsten) of the concave container or the metal layer (nickel plating) of the sealing plate is covered with the conductive paste, the electrolyte that has passed through the holes or holes may come into contact with the metal.

  Such a problem occurs not only in the electric double layer capacitor but also in an electrochemical cell constituting another type of electronic component such as an ion capacitor or a nonaqueous electrolyte battery.

JP 2001-216852 A JP 2012-44074 A

  The object of the present invention is to minimize the amount of elution due to an applied voltage by contacting an electrolyte with a metal layer through an electrode.

(1) In invention of Claim 1, it is comprised from the concave container and the sealing board, The container which has a cavity part, The 1st metal layer formed in the bottom of the said concave container in the said cavity part, The said, A first electrode disposed in the cavity and the first electrode are electrically connected to the first metal layer, and the first electrode is disposed on the inner bottom surface of the concave container. 1 current collector, a second metal layer formed on the cavity side of the sealing plate, a second electrode disposed in the cavity at a predetermined distance from the first electrode, A second current collector for electrically connecting the second electrode to the second metal layer and disposing the second electrode on the sealing plate, the first electrode, and a second electrode An electrolyte impregnated in the electrode, and at least one of the first current collector and the second current collector is made of carbon as a conductive material. The first layer current collector and the second layer current collector, and the conductivity between the first layer current collector and the second layer current collector, which are formed by fat, are cut off from the electrolyte. And a blocking layer having an electrochemical resistance to the electrolyte , and the sealing plate includes an outer peripheral flat plate portion connected to the concave container, a central flat plate portion, and an inner periphery of the outer peripheral flat plate portion. And an annular groove portion that continuously connects the outer periphery of the central flat plate portion, and the second metal layer, the second current collector, and the second electrode are disposed on the central flat plate portion . An electronic component is provided.
(2) In the invention described in claim 2, the block layer is composed of an aluminum layer and a carbon layer formed on the surface on the first electrode side. The electronic component described is provided.
( 3 ) In the invention described in claim 3 , the second metal layer, the second current collector, and the second electrode are arranged in a recess formed by the annular groove portion and the central flat plate portion. The electronic component according to claim 1 , wherein the electronic component is provided.
(4) In the invention described in claim 4, the electronic component according to any one of claims of claims 1 to 3, and storage means for storing electric to the electronic component, a predetermined function There is provided an electronic apparatus comprising: another electronic component to be exhibited; and power supply means for supplying electric power to the other electronic component using the stored charge.

  According to the present invention, since the block layer is provided in the middle of the thickness direction of the current collector for fixing the inner bottom surface of the concave portion and the sealing plate and the electrode, the permeation of the electrolyte from the electrode can be further reduced.

It is explanatory drawing showing the current collection coupling layer which electrically couples a concave container, a sealing board, an electrode (anode), and an electrode (cathode) in an electric double layer capacitor. It is a figure for demonstrating the electric double layer capacitor which concerns on embodiment. It is a figure for demonstrating the method of forming a collector in the sealing board in embodiment. It is a figure for demonstrating a part of method of forming an electrical power collector in the concave container in embodiment. It is a figure for demonstrating the remainder of the method of forming a collector in the concave container in embodiment. It is explanatory drawing which attaches a sealing board to a concave container, and joins an electric double layer capacitor. It is a figure for demonstrating each modification by the side of a concave container. It is a figure for demonstrating the modification by the side of a sealing board. It is a figure for demonstrating the other modification of the sealing board side. It is a figure for demonstrating the modification with respect to the penetration electrode of a concave container. It is explanatory drawing showing each process of the manufacturing method of a pre-assembly unit. It is a figure for demonstrating the modification about a collector and a block layer. It is a figure for demonstrating the conventional electric double layer capacitor.

The electrochemical cell constituting the electronic component of the present embodiment will be described with reference to the drawings by taking an electric double layer capacitor as an example.
(1) Outline of Embodiment FIG. 1 shows a current collecting coupling that electrically couples the concave container 2, the sealing plate 3, the electrode 6 (anode), and the electrode 5 (cathode) in the electric double layer capacitor of the present embodiment. This is a representation of the layer.
In FIG. 1, with the one-dot chain line in the center as a ridge, the right side represents the configuration on the concave container 2 side, and the left side represents the configuration on the sealing plate 3 side. Thus, since the current collecting coupling layer of the concave container 2 and the sealing plate has the same configuration, the same number is attached to each part constituting both current collecting coupling layers as a reference to the concave container 2 side. Is attached with a subscript a, and a subscript b is attached on the sealing plate 3 side.
In FIG. 1, in order to compare the concave container 2 side and the sealing plate 3 side, they are displayed side by side, but actually, as shown in FIG. 2A, the electrodes 5 and 6 face each other. Are arranged as follows.
FIG. 1 shows the case where the thicknesses of the electrode 6 (anode) and the electrode 5 (cathode) are the same. However, the electrode 6 and the electrode 5 have a thickness and a length in order to adjust the capacity balance. Can be of different dimensions.

As shown in FIG. 1, the electric double layer capacitor of the present embodiment includes a concave container 2 and a sealing plate 3 as a housing that accommodates the capacitor.
The concave container 2 is formed by firing ceramics using alumina at a high temperature (for example, 1000 degrees or more), and has a concave portion 13. A metal layer (tungsten) 11 (not shown) that can withstand the firing temperature of the concave container 2 is formed on the inner bottom of the concave portion 13. On the metal layer 11 (on the sealing plate 3 side), a first current collector comprising a current collector 181a using carbon as a conductive material, a block layer 50a, and a current collector 182a is formed, and an electrolyte is impregnated thereon. The electrode (anode) 6 is fixed.
On the other hand, the sealing plate 3 is made of an alloy such as Kovar. A metal layer 15 (not shown) is formed on the entire surface of the sealing plate 3 by nickel plating, and is formed on the metal layer 15 (on the concave container 2 side). , A second current collector composed of a current collector 181b using carbon as a conductive material, a block layer 50b, and a current collector 182b is formed, and an electrode (negative electrode) 5 impregnated with an electrolyte is fixed thereon.
Note that the sealing plate 3 may be prepared by preparing a base material of the sealing plate 3 and a plate material to be a material of the metal layer 15 in advance, processing the clad material, and press-molding it. This eliminates the need for nickel plating.
The block layers 50a and 50b are formed of aluminum layers 51a and 51b whose surfaces are pre-coated with carbon layers 52a and 52b. The carbon layer may be formed on both surfaces of the block layers 50a and 50b.

In the present embodiment, the blocking layers 50a and 50b that block the passage of the electrolyte are arranged between the current collectors 182a and 182b on the electrodes 6 and 5 side and the current collectors 181a and 181b on the concave container 2 and the sealing plate 3 side. It is arranged.
Therefore, when the current collectors 181a, 182a, 181b, and 182b are formed by heating and solidifying the conductive paste, the electrodes 6 and 5 are impregnated even if holes or holes are formed. Since the electrolyte is blocked by the block layers 50a and 50b, the metal 11 and 15 formed on the concave container 2 and the sealing plate 3 are prevented from contacting each other.

In the example shown in FIG. 1, meniscuses 191a and 101b are formed at the peripheral portions of the current collectors 181a and 181b. This is formed by sandwiching the conductive paste dropped as the current collectors 181a and 181b between the sealing plate 3 and the concave container 2 and the aluminum layers 51a and 51b.
Thus, when the peripheral edges of the current collectors 181a and 181b are in an open state (a state where they are not in contact with other walls or the like), meniscuses 191a and 191b that are recessed in the central direction at the peripheral edge are formed, so that the conductive paste It is possible to prevent the aluminum layers 51a and 51b from having the same size as the aluminum layers 51a and 51b.
By forming such concave meniscuses 191a and 191b on the periphery, the current collectors 181a and 181b having a desired size can be formed, so that defects due to protrusion of the current collectors 181a and 181b can be avoided. .

(2) Details of Embodiment FIG. 2 (a) is a side sectional view of the electric double layer capacitor 1 according to the embodiment, FIG. 2 (b) is a plan view, and FIG. 2 (c) is a sealing with an electrode 5 attached. FIG. 3 is a cross-sectional perspective view of a plate 3.
As shown in FIG. 2B, the electric double layer capacitor 1 has a rectangular parallelepiped shape, and the size is, for example, a height of 1 [mm] or less and a length of about 2.5 [mm]. It has a rectangular parallelepiped shape with a width of about 3.0 [mm].
Note that the outer shape of the electrochemical cell including the electric double layer capacitor 1 may be a circle or an ellipse as viewed from above. In this case, each part such as the concave portion 13, the electrodes 5, 6 and the separator 7 described as a square may be circular or elliptical, or may be square.

The electric double layer capacitor 1 includes a concave container 2 having a concave portion 13, a sealing plate 3 having a metal layer 15 formed on the lower surface (the concave container 2 side) (thickness is about 0.1 [mm]), An electrode 5 used as a negative electrode, an electrode 6 used as a positive electrode, a separator 7, a bonding metal layer 8, a metal layer 11,
Current collectors 181a and 182a, block layers 50a and 50b, current collectors 181a and 182b, through electrode 21, through electrode 22, terminal 10, terminal 12, and electrolytes impregnated in electrodes 5 and 6 and separator 7 (FIG. Etc.).
The terminals 10 and 12 are terminals for surface mounting. In the following description, the terminals 10 and 12 are referred to as the downward direction, and the sealing plate 3 side is referred to as the upward direction.
In FIG. 2A, a gap is illustrated between the electrode 5, the separator 7 and the electrode 6 so that the joining relationship of the members can be easily understood. However, these members may be packed in the recess 13 without any gap. .

The concave container 2 is made of ceramics using alumina, for example, and is formed by stacking and integrating a plurality of flexible ceramic sheet materials 41 to 45 called green sheets. The thickness of each sheet after baking can be 100-300 micrometers. In addition, it is desirable that the thicknesses are the same, because the labor and time for preparing the sheet are reduced. In Fig.2 (a), the junction part of the sheet | seat materials 41-45 is shown with the broken line.
The green sheet has openings corresponding to the recesses 13 and the reservoirs 17 and holes corresponding to the through holes in which the through electrodes 21 and 22 are installed. These green sheets are laminated in the thickness direction and fired. Thereby, the concave container 2 having the concave portion 13 and the through holes for the through electrodes 21 and 22 is formed. Here, the diameter of the through electrode can be about 100 μm. In addition, a conductive printing made of tungsten (W) is previously formed on the upper surface of each green sheet for the purpose of absorbing the error when the through electrode 21 and the through electrode 22 formed in each layer are misaligned when the green sheets are stacked. Can be applied.

  More specifically, the sheet materials 41 and 42 are formed with through holes corresponding to the shape of the through electrodes 21 and 22, and the sheet material 43 has a through hole and a storage portion corresponding to the shape of the through electrodes 21. An opening corresponding to the shape of the through electrode 21 and an opening corresponding to the shape of the recess 13 are formed in the sheet materials 44 to 45.

The concave portion 13 has a rectangular cross section when viewed from above, and a concave storage portion 17 having a metal layer 11 formed on the bottom surface is formed at the bottom of the concave portion 13.
The metal layer 11 is formed by conducting conductor printing on the surface of the sheet material 42 corresponding to the bottom surface of the storage portion 17 and firing the concave container 2.
Here, the size of the metal layer 11 is reduced to the minimum necessary to reduce the cost. Note that the metal layer 11 may be formed on the entire bottom surface of the reservoir 17.
The conductor printing of the metal layer 11 is performed by screen printing with an ink containing a high melting point metal material that has corrosion resistance such as tungsten and can withstand firing of the concave container 2.

Tungsten is suitable as an electrode to be formed in the recess 13 because it has a high melting point, is difficult to oxidize, has moderate adhesion extremes with the ceramic surface, and has practical electrical resistance after firing.
However, as described above, when tungsten is used as the positive electrode current collector and is always in contact with the electrolyte impregnated in the electrode 6, the voltage is applied to the electrolyte, and the electrolyte is electrochemically dissolved.
Therefore, in this embodiment, in order to prevent elution of the metal layer 11 formed of a metal such as tungsten that can withstand firing, the entire surface facing the electrode 6 impregnated with at least an electrolyte (in this embodiment, a wider surface). Is covered with current collectors 181a and 182a made of conductive paste.
Furthermore, in this embodiment, in order to prevent the electrolyte from reaching the metal layer 11 through the holes or holes generated in the current collectors 181a and 182a, between the current collector 181a and the current collector 182a, A block layer 50a that blocks passage of electrolyte is provided.

The block layer 50a is made of a material that has conductivity and has a blocking property to block the permeation of the electrolyte impregnated in the electrode 6 and an electrochemical resistance.
Here, “electrochemical resistance” refers to resistance to electrochemical oxidation or reduction even when the electrolyte is in contact and the electrode potential during charging / discharging reaches the oxidation potential or reduction potential. It means doing.
In this embodiment, the block layer 50a is formed by the aluminum layer 51a whose surface is pre-coated with the carbon layer 52a. However, the carbon layer 52a is omitted and only the aluminum layer 51a has the above-described conductivity, barrier property, and resistance. It is possible to obtain. Further, the block layer 50a in which the carbon layer 52a is precoated on both surfaces of the aluminum layer 51a may be used.
In addition to aluminum, other metals (for example, titanium, niobium, stainless steel, gold) and resins having conductivity, barrier properties, and electrochemical resistance may be used.

In the present embodiment, the block layer 50a having these three properties is disposed between the current collector 182a on the electrode 6 side and the current collector 181a on the concave container 2 side.
Therefore, even when the current collectors 181a and 182a are formed by heating and solidifying the conductive paste, the electrolyte impregnated in the electrode 6 is blocked by the block layer 50a even if holes or holes are formed. Therefore, contact with the metal 11 formed in the concave container 2 is avoided.

Here, the relationship between the sizes of the current collectors 181a and 182a and the block layer 50a (planar size) with respect to the sizes of the electrode 6 and the metal layer 11 will be described.
The size S2 of the current collector 181a is not less than the size S1 of the metal layer 11 because it is necessary to cover the metal layer 11.
Since the size S3 of the block layer 50a needs to block the electrolyte from reaching the metal layer 11, it should be equal to or larger than the size S1 of the metal layer 11, and the entire surface of the metal layer needs to face the block layer 50a. .
The size S4 of the current collector 182a and the size S5 of the electrode 6 may be almost the same size as the size S3 of the block layer 50a, but as shown in FIG. 2, the block layer 50a is formed larger than the current collector 182a. It is also possible to do.
However, in the present embodiment, as shown in FIG. 2, the metal layer 11 is formed small to a minimum size necessary for cost reduction, whereas the current collector 181 a is the entire bottom surface of the storage unit 17. The current collector 182a and the block layer 50a are formed to have substantially the same size as the size S5 of the electrode 6.

The thickness of the current collectors 181a and 182a is set to a predetermined thickness that does not affect the metal layer 11 due to the electrolyte impregnated in the electrode 6, and is adjusted when the conductive paste is applied. .
Specifically, the predetermined thicknesses of the current collectors 181a and 182a are usually set in the range of 5 to 100 μm, preferably 10 to 40 μm.
When the thickness after application of each current collector 181a, 182a is thin (less than 10 μm), the electrical resistance varies widely and generally tends to be high, so the thickness is set to 10 μm or more. In addition, when the thickness is too thick, the overall electric resistance is increased and the thickness of the electric double layer capacitor 1 is affected. Therefore, the thickness is set to 100 μm or less, preferably 40 μm or less.
The method of coating the conductive paste film is by transfer, screen printing, ink jetting, coating with a dispenser, podding, or the like.

The conductive paste is applied to the entire bottom surface of the storage portion 17 to form a concave meniscus shape along the inner side wall surface by its surface tension, but the thickness of the central portion of the liquid paste is flattened. There is also an effect that.
Electrochemically, electrons tend to concentrate at the sharp tip of the conductor. When charging / discharging the electrochemical device, if electrons concentrate on the sharp tip of the conductor, there is a concern that power concentrates only around the tip of the conductor and deterioration is accelerated.
Therefore, by applying the paste of the present invention, it can be expected that the sharp portion is eliminated and the concentration of electrons is eliminated, thereby preventing the deterioration of the electrode.

Although the metal layer 11 has a thickness, the thickness of the metal layer 11 is made uniform by the conductive paste, and current collectors 181a and 182a having flat surfaces are obtained.
The conductive paste is a paste made by adding a solvent to a carbon material and an organic material (hereinafter described as an example of a phenolic resin, but not limited to a phenolic resin) and adding a solvent. Use (can). The carbon material is added to impart conductivity. As the carbon material, any of graphite powder, amorphous carbon (carbon black), or a mixture of both can be used.
When the solvent is dried by heating and the phenolic resin component is polymerized (solidified), resin-made current collectors 181a and 182a having a phenolic resin as a binder and carbon as a conductor are formed.

Here, in the electrochemical device, generally in the case of the current collector of the negative electrode, nickel, copper, brass, zinc, tin, gold, stainless steel, tungsten, aluminum, can be used many metals, the electric double layer capacitor In the negative electrode current collector, copper, gold, stainless steel, and aluminum are preferably used, and the positive electrode current collector is made of aluminum, titanium, niobium, or the like in order to prevent the current collector from being dissolved into the electrolyte. It is necessary to use a metal called plug metal. As the positive electrode current collector, carbon other than these metals can be used. In this embodiment, a conductive paste containing a carbon material is used. When a conductive paste is used, it is not necessary to form a plug metal thin film by vacuum deposition or the like, so that the process is greatly simplified.

The conductive paste is a mixture of graphite, which is highly crystalline among carbons, and amorphous carbon black among carbons, and further contains a binder mainly composed of a phenolic resin. For this phenolic resin, an aldehyde represented by formaldehyde and a derivative containing phenol can be used. Moreover, water glass, an epoxy, etc. can be used besides a phenol-type resin.
In addition to the conductive filler, it is desirable to add a nonconductive material for adjusting the thermal expansion coefficient to the conductive paste. In this case, an appropriate amount of various glass powders, silica (SiO 2), alumina (Al 2 O 3), titania (TiO 2), etc. can be used as the non-conductive material.

  Although the conductive paste has a viscosity of about 400 dPa · s, it has poor workability and can be diluted with a low-boiling solvent such as thinner. By this dilution, the viscosity can be reduced to about 40 dPa · s or less. In this way, when considering the workability, when the viscosity of the conductive paste is lowered, the conductive paste crawls up the wall surface with a solvent, and the wall surface becomes conductive when dried and solidified in the crawl-up state. In this state, there is a risk of short-circuiting when the electrodes are stacked, but there is an effect of avoiding this.

The reservoir 17 is formed at the center of the bottom of the recess 13, the depth of the reservoir 17 is set smaller than the thickness of the electrode 6, and the inner periphery of the reservoir 17 is more conductive paste than the outer periphery of the electrode 6. The meniscus 192a is set to be large. The reservoir 17 is provided to prevent the conductive paste from scattering or protruding before solidifying and causing a short circuit.
The storage part 17 functions as a storage part for holding a conductive paste (after solidification, the current collector 181a) formed of insulating sheet materials 42 and 43.

Here, the meniscus 192a is a concave surface generated on the surface of the conductive paste due to surface tension when the conductive paste is stored in the storage portion 17.
When the electric double layer capacitor 1 is manufactured, when the liquid conductive paste is stored in the storage portion 17 and the block layer 50a is placed on the surface thereof, the block layer 50a is positioned at the center of the storage portion 17 by the meniscus 192a. .
On the block layer 50a, a second layer of conductive paste (after solidification, a current collector 182a) is applied, and an electrode 6 is disposed on the second layer of conductive paste.
Thereafter, when the conductive paste is solidified by heating, current collectors 181a and 182a are formed, and the electrode 6 is firmly fixed to the center of the storage portion 17 via the current collectors 181a and 182a.
As described above, in the present embodiment, the formation of the positive electrode current collectors 181a and 182a does not require a dry process such as vacuum vapor deposition, so that the manufacturing cost of the electric double layer capacitor 1 can be reduced and the productivity can be improved. .

  The electrode 6 is formed by forming an electrode active material mainly composed of activated carbon into a sheet and cutting it into a rectangle. For example, a natural material is coconut husk, and an artificial material is a coal pitch, petroleum pitch or phenolic material. Resin carbides that are activated with water vapor, chemicals, or electrochemistry are used.

Under the concave portion 13 of the concave container 2, by laminating the sheet materials 41, 42 having holes as described above, through holes having openings on the bottom surface of the concave portion 13 and the bottom surface of the concave container 2 are formed. Is formed.
A cylindrical through electrode 22 that electrically connects the metal layer 11 and the terminal 12 is formed in the through hole.
The outer diameter of the through electrode 22 and the inner diameter of the through hole are set to be the same, and no gap is generated between the through electrode 22 and the inner wall of the through hole. The through electrode is also referred to as VIA.

  The diameter of the through electrode 22 is about 0.1 to 0.3 [mm]. Further, intermediate electrodes 28 are provided by conductor printing between the layers of the respective sheet materials. For example, the through electrode 22 can be reliably formed by the intermediate electrode 28 even when the accuracy of the through hole is insufficient or the lamination of the sheet material is shifted. The configuration of the through electrode 21 described later is also the same.

  The through electrode 22 is filled with a metal paste mainly composed of a metal powder such as tungsten in this through hole and sintered, or a conductive paste such as carbon is injected and solidified, or a metal bar. Or by inserting a plate material. As the metal bar, for example, aluminum, stainless steel, tungsten, nickel, silver, gold, or a conductive resin containing carbon can be used. The electrode 6 is electrically connected to the terminal 12 through the metal layer 11 and the through electrode 22.

A metal layer 9 and a bonding metal layer 8, which are metal layers for bonding the sealing plate 3 and the concave container 2, are formed at the end of the opening of the recess 13.
The bonding metal layer 8 can be formed of nickel, and can be formed on the metal layer 9 (metallized layer) formed on the entire periphery of the end of the opening. In addition, a seal ring made of Kovar is attached to the metal layer 9 (metallized layer) through a brazing material (nickel, gold, silver, silver-copper, etc.) layer, and a joining metal layer 8 is formed thereon. You can also The bonding metal layer 8 is for ensuring airtightness between the sealing plate 3 and the concave container 2.

The metal layer 9 (metallized layer) is formed by tungsten conductor printing and can be formed at the time of firing the ceramic, and an alloy having a ratio of Kovar (Co: 17, Ni: 29, Fe: 54) through a brazing material. ) Is placed on the metal layer 9 (metallized layer), and a metal ring made of Kovar is placed at the end of the concave container 2 to melt and weld the brazing material, and thereafter The bonding metal layer 8, for example, pure nickel, nickel added with phosphorus, nickel added with boron, or the like can be formed by plating or the like.
As will be described later, when the sealing plate 3 formed with the metal layer 15 is placed in the opening of the recess 13 and heated, the bonding metal layer 8 is melted and fused with the metal layer 15, and the recess 13 is formed by the sealing plate 3. Sealed.

In the concave container 2, by laminating sheet materials 41 to 45 having holes, through-holes having openings at the end of the opening of the concave 13 and the bottom of the concave container 2 in the side wall surrounding the concave 13 Is formed.
A cylindrical through electrode 21 that electrically connects the bonding metal layer 8 and the terminal 10 is formed in the through hole.
The outer diameter of the through electrode 21 and the inner diameter of the through hole are set to be the same, and no gap is generated between the through electrode 21 and the inner wall of the through hole.
The material and forming method of the through electrode 21 and the bonding using the intermediate electrode 28 are the same as those of the through electrode 22.

The terminals 10 and 12 are formed by conducting conductor printing with an ink containing tungsten or the like and firing it, and then plating the surface thereof with gold or nickel. Furthermore, a metal such as gold or tin can be plated on the nickel plating for rust prevention.
The plating includes electrolytic plating and electroless plating, and may be formed by a vapor phase method such as vacuum deposition.
Thereby, the high solder wettability of the terminals 10 and 12 is ensured, and the electric double layer capacitor 1 can be satisfactorily surface-mounted on the substrate.
In addition, in this embodiment, although the terminals 10 and 12 were provided in the outer bottom face part of the concave container 2, you may form in an outer side face part, or may form continuously from an outer bottom face to a side face.
The terminals 10 and 12 can be formed after the through electrodes 21 and 22 are installed in the through holes. However, in this embodiment, the molybdenum layer serving as the base is printed almost simultaneously with the VIA (through electrode) and is fired. After that, plating is performed.
Further, as will be described later, when a large number of concave containers 2 and electric double layer capacitors 1 are formed at the same time with a large sheet material, the portion corresponding to the cut portion load after the formation, that is, the outside of the bottom of the concave container 2 is formed. By preventing the terminals 10 and 12 from being formed up to the end portions, it is possible to prevent the terminals 10 and 12 from peeling off when being divided (separated). As described above, when a plurality of large sheets are formed and then divided, the terminals 10 and 12 may be plated before the division.

The sealing plate 3 is a metal member made of Kovar or the like. Since Kovar has a thermal expansion coefficient approximately equal to that of ceramics, it is possible to suppress the stress generated between the sealing plate 3 and the concave container 2 when the electric double layer capacitor 1 is heated during reflow.
As shown in FIGS. 2B and 2C, the sealing plate 3 is configured such that both the flat surfaces are curved outward (one side) in the central region corresponding to the electrode 5, so Is formed, and the electrode 5 is accommodated and fixed in the storage portion 310 (recess).
Similar to the reservoir 17 formed in the recess 13, the reservoir 310 is provided to prevent the conductive paste from scattering or protruding before solidifying and causing a short circuit.

The reservoir 310 is formed in a rectangular shape that is set larger than the shape of the electrode 5 by about the meniscus 192b of the conductive paste. The recess of the storage part 310 is formed by pressing the sealing plate 3.
And the metal layer 15 by nickel plating is formed in the whole lower surface of the sealing board 3 including the dent by this storage part 310. FIG. Since the metal layer 15 is formed in order to satisfactorily bond the sealing plate 3 to the bonding metal layer 8, it does not necessarily have to be formed over the entire surface of the sealing plate 3, and at least the annular metal layer The metal layer 15 may be formed in an annular shape with a predetermined width on the portion corresponding to 8, that is, on the outer peripheral side of the sealing plate 3.
The metal layer 15 may be formed by plating a metal. In addition to wet plating, a dry process such as sputtering or thermal spraying can be used.
As a plating material, nickel (Ni), copper (Cu), tin (Sn), zinc (Zn), phosphorus (P), boron (B), or a material containing them at the same time, for example, copper and tin These alloys can be used. Moreover, you may have a density | concentration gradient in the lower surface of the surface. At this time, the atomic ratio of copper and tin can be in the range of Cu: Sn = 80: 20 to 1:99.
In particular, the Cu: Su ratio is desirably 55:45 to 1:99.
When an atomic concentration gradient is provided, a nickel rich layer is formed on the lowermost surface (side in contact with the sealing plate), and then a copper rich layer, followed by a tin rich layer (Sn), and further zinc (Zn ) And a concentration gradient.
For example, alloy plating of nickel (Ni) and zinc (Zn) or alloy plating of tin (Sn) and zinc (Zn) can be used.
At that time, the plating is performed by batch-processing the strip-shaped metal (hoop material) by a continuous plating method or by using a device such as a barrel after punching the strip-shaped metal (hoop material). You can also.
The thickness of the plating layer is preferably 0.2 μm or more, and more preferably 0.6 μm or more. Further, when plating with a barrel or the like, pinholes or the like may be generated, and the average film thickness of plating is preferably 5 μm or more. However, even if plating of 10 μm or more is used, only the cost is increased, and no improvement effect is observed when welding.

In the recess of the sealing plate 3 by the storage part 310, at least the entire surface facing the electrode 5 impregnated with the electrolyte (in this embodiment, the entire recess of the storage part 310, which is a wider surface) is collected by the conductive paste. A body 181b, a block layer 5b, and a current collector 182b are formed. The electrode 5 made of an electrode active material is firmly fixed in the reservoir 310 by the three layers of the current collector 181b, the block layer 5b, and the current collector 182b.
The current collectors 181b and 182b are formed in the same manner with the same thickness using the same conductive paste as the conductive paste constituting the current collectors 181a and 182a, and the block layer 50b is also formed with the block layer 50a. By being formed in the same manner, the electrode 5 is fixed to the sealing plate 3 (metal layer 15).

That is, when a conductive paste (current collector 181b after solidification) is applied to the entire bottom surface (recessed portion) of the reservoir 310 and the block layer 50b is placed on the surface, the block layer 50b is formed by the meniscus 192b. It is positioned at the center of the recess of the storage unit 310.
On the block layer 50b, a second layer of conductive paste (after solidification, the current collector 182b) is applied, and the electrode 5 is disposed on the second layer of conductive paste.
Thereafter, when the conductive paste is solidified by heating, the current collectors 181b and 182b are formed, and the electrode 5 is firmly fixed to the center of the recess of the storage portion 310 via the current collectors 181b and 182b.
Thus, like the concave container 2, the blocking layer 50 b is disposed between the current collector 181 b and the current collector 182 b for fixing the electrode 5 to the metal layer 15 (sealing plate 3), whereby the electrode 5 The electrolyte impregnated in can be effectively cut off.

  The block layer 50b is formed of an aluminum layer 51b whose surface is pre-coated with a carbon layer 52b, like the block layer 50a. However, the carbon layer 52b may be omitted and only the aluminum layer 51b may be used. Carbon layers 52b may be precoated on both sides of 51b. In addition to aluminum, other metals (for example, titanium, niobium) and resins having conductivity, barrier properties, and electrochemical resistance may be used.

As for the sealing plate 3, unlike the concave container 2 made of ceramics, the entire surface on the concave container 2 side is a metal (metal layer 15 or metal forming the sealing layer 3 with the metal layer 15). For this reason, the size of the blocking layer 50 b is not defined by the size of the metal of the sealing plate 3, but is formed to be larger than the size of the electrode 5.
The current collector 182 b is formed to have almost the same size as the electrode 5.

The sealing plate 3 in which the electrode 5 is fixed to the storage portion 310 by the current collector 18b is brazed to the bonding metal layer 8 so that the sealing plate 3 is physically attached to the opening of the recess 13 and Electrically joined.
The brazing is dissolved by heating the sealing plate 3 while applying pressure, and the sealing plate 3 and the concave container 2 are joined.
More specifically, it is possible to use parallel seam welding in which the roller electrode is brought into contact with the edge of the sealing plate 3 with an appropriate pressure and is rotated while being energized. The bonding metal layer 8 is heated by the contact resistance, and pressurization and heating are performed. In addition to parallel seam welding, heat welding by laser is also possible.

When performing parallel seam welding, it is desirable to select a material with good compatibility between the bonding metal layer 8 and the sealing plate 3. For example, when electrolytic nickel or electroless nickel is used for the bonding metal layer 8, the sealing plate 3 is , Kovar with electrolytic nickel or electroless nickel is used.
Or, conversely, when electrolytic nickel is used for the bonding metal layer 8, the sealing plate 3 is obtained by applying electroless nickel to Kovar. Thereby, it is not necessary to raise the welding power more than necessary. Furthermore, when performing electroless nickel, various reducing agents can be used. Examples include dimethylamine borane, hypophosphorous acid, hydrazine, sodium borohydride and the like. Here, when the nickel used for plating is melted as the brazing material, it is desirable that the melting point of nickel is lower. Therefore, by using hypophosphorous acid as a reducing agent during plating, when the chemical composition of the finished plating is “Ni: 90% -96%, P: 4% -10%”, boron Compared to the case of containing, it has a lower melting point and is suitable for brazing.
Further, in order to fix the seal ring of the bonding metal layer 8 to the ceramic metallized layer, it is also possible to use a brazing material such as gold brazing or silver brazing or a solder material.

  The metal layer 15 of the sealing plate 3 is brazed to the bonding metal layer 8 in this way, so that the electrode 5 has the current collector 181b, the block layer 50b, the current collector 182b, the metal layer 15, the bonding metal layer 8, It is electrically connected to the terminal 10 through the through electrode 21.

The electrodes 5 and 6 face each other in a cavity formed by the recess 13 and the sealing plate 3, and a separator 7 is installed between the electrodes 5 and 6 to prevent a short circuit due to contact of the electrodes 5 and 6. Has been.
As the material of the separator 7, for example, a microporous film having many pores in PTFE (polytetrafluoroethylene) resin is used, and further, PPS (polyphenylene sulfide), PEEK (polyetheretherketone), modified PEEK, A nonwoven fabric made of a material having hydrophilicity on the surface thereof, such as a heat resistant resin, or a glass fiber can be used. Cellulosic separators may also be used.
The separator 7 preferably has a function of preventing a short circuit between the electrode 5 and the electrode 6 and a function of containing more electrolyte, that is, a function of retaining a high electrolyte. Although PTFE is used as the separator 7 of this embodiment, glass fiber is most desirable from the viewpoint of the liquid retention function.

  Moreover, as a shape of the separator 7, it is good also as a shape where the outer peripheral part curves to the upper side or the lower side. In this case, the separator 7 is disposed so that the inner side surface of the curved outer peripheral portion faces the side surface of the electrode 5 or the electrode 6. Thereby, the contact with the electrode 5 and the electrode 6 can be avoided more reliably.

An electrolyte is sealed in the cavity formed by the recess 13 and the sealing plate 3 in a state where the electrodes 5 and 6 and the separator 7 are impregnated.
The electrolyte is composed of a solution in which a supporting salt such as (CH ₃ ) · (CH ₄ ) ₃ N · BF ₄ is dissolved in a nonaqueous solvent such as PC (propylene carbonate) or SL (sulfolane). As described above, in the present embodiment, a liquid is used as the supporting salt, but a gel-like or solid electrolyte can also be used. Although depending on the sealing method, when a liquid solvent is used as the electrolyte, the boiling point is desirably 200 ° C. or higher. Furthermore, it is desirable that the vapor pressure does not increase due to the heat applied during sealing. A low boiling point solvent having a boiling point of less than 100 ° C. can be added to the electrolytic solution, but at least the vapor pressure at the melting point of the resin is preferably 0.2 MPa-G or less. When injecting the electrolytic solution, the electrolyte can be impregnated into the details of the electrodes 5 and 6 by injecting the electrolytic solution into the concave portion 13 and then singly or in combination with reduced pressure, heating, or increased pressure.

The electric double layer capacitor 1 configured as described above is surface-mounted on a substrate with the terminal 10 as a negative electrode and the terminal 12 as a positive electrode, and can be used as, for example, a mobile phone memory or a clock backup power source.
In this case, the mobile phone charges the electric double layer capacitor 1 at the same time that the battery of the main power source is mounted, and the electric charge accumulated in the electric double layer capacitor 1 is changed when the battery is replaced or when the voltage of the main power source decreases. Is discharged to supply power to the memory or to maintain a function such as a clock.
In addition, power storage elements for energy generation using energy harvesting, wireless sensor networks, RFID tags, power supplies such as RF remote controls for digital home appliances, power storage elements, contactless IC cards, power supplies for multi-function IC cards, power storage elements, instantaneous interruption It can also be applied and used for backup of CPU and DRAM, power supply for saving data to flash memory, power storage element, etc.

Next, the formation of the current collectors 181a and 182a, the blocking layer 50a, the current collectors 181b and 182b, and the blocking layer 50b and a method for assembling the electric double layer capacitor 1 will be described.
FIG. 3 is a view for explaining a method of forming the current collectors 181b and 182b and the blocking layer 50b on the sealing plate 3. FIG.
First, as shown in FIG. 3A, a sealing plate 3 having a storage portion 310 is formed by pressing a rectangular plate made of Kovar. Then, the metal layer 15 is formed by performing nickel plating on the entire surface on the concave side.

  And as shown in FIG.3 (b), the recessed side of the sealing board 3 is turned up, and the electrically conductive paste used as the electrical power collector 181b is supplied to the storage part 310 only a predetermined amount. The supply amount of the conductive paste is set so as to fill all of the bottom surface of the storage portion 310, the meniscus 192b is formed on the outer peripheral portion, and the above-described predetermined thickness.

Next, as shown in FIG. 3C, the block layer 50b is placed on the liquid surface of the conductive paste to be the current collector 181b. Although the block layer 50b is not shown, a carbon layer 52b is formed on the upper surface of the aluminum layer 51b (the side opposite to the sealing plate 3 side).
Next, as shown in FIG. 3D, a predetermined amount of a second layer of conductive paste to be the current collector 182b is supplied to the upper surface of the block layer 50b.
Further, as shown in FIG. 3E, the electrode 5 is placed on the upper surface of the second layer conductive paste.
Thereafter, for example, in the case of a phenol resin, heat treatment is performed at a temperature of about 150 [° C.], whereby the two layers of the conductive paste are solidified to form current collectors 181b and 182b with the block layer 50b interposed therebetween, and the electrode 5 is A component on the side of the sealing plate 3 in which the electrode 5 is fixed by the current collector 181b, the block layer 50b, and the current collector 182b is firmly fixed to the central portion of the reservoir 310.

After the parts on the sealing plate 3 side are completed, the electrode 5 is impregnated with an electrolyte at a stage before brazing the concave container 2.
However, instead of impregnating the electrode 5 with the electrolyte in advance, the electrode 5 may be impregnated when the sealing plate 3 is set in the concave container 2 for brazing. That is, when the electrode 6 of the concave container 2 is impregnated with the electrolyte, not only the amount of the electrode 6 and the separator 7 impregnated but also the electrolyte for the electrode 5 is injected into the concave portion 13 (the electrolyte is between the concave portion and the electrode 6). To be satisfied). Then, the electrode 5 may be impregnated with the electrolyte by capillary action by setting the component on the sealing plate 3 side in the concave container 2.

In addition, you may make it manufacture the several sealing board 3 at once by forming the several storage part 310 in the press material of a large Kovar board | plate, and cut | disconnecting to the size of the sealing board 3 after that.
Furthermore, you may cut | disconnect, after forming the metal layer 15 in the storage part 310 which carried out multiple press molding. Here, you may make it give the additional press process for crushing a burr | flash to the cut | disconnected components.
In addition, after the metal layer 15 is formed in the plurality of press-molded storage portions 310, the supply of the two layers of conductive paste, the arrangement of the block layers 50b, and the electrodes 5 are disposed in each storage portion 310, and the heat treatment is performed. You may make it cut | disconnect to the individual sealing board 3. FIG.

Each of FIGS. 4 to 6 is a diagram for explaining a method of forming the current collector 181a, the block layer 50a, the current collector 182a, and the electrode 6 in the concave container 2 after firing.
First, as shown in FIG. 4A, a concave container 2 in which the bonding metal layer 8, the metal layer 9, the through electrodes 21 and 22, the metal layer 11, and the terminals 10 and 12 are formed is prepared.
And the electrically conductive paste used as the electrical power collector 181a is supplied to the storage part 17. FIG. The supply amount of the conductive paste is set such that the entire bottom surface of the storage portion 17 is filled and the meniscus 19a is formed.

FIG. 4B is a view of the concave container 2 as viewed from above before supplying the conductive paste to the storage unit 17. As shown in FIG. 4B, the metal layer 11 is formed in a circular shape at the bottom of the storage portion 17. The shape of the metal layer 11 may be arbitrary such as a rectangle.
FIG. 4C is a view of the conductive paste supplied to the concave container 2 as viewed from above.
A conductive paste serving as a current collector 181 a is stored in the center of the concave container 2.

Next, as shown in FIG. 5A, the block layer 50a is placed on the liquid surface of the conductive paste that becomes the current collector 181a. Although this block layer 50a is not shown, a carbon layer 52a is formed on the upper surface (sealing plate 3 side) of the aluminum layer 51a.
Next, as shown in FIG. 5B, a predetermined amount of the second-layer conductive paste to be the current collector 182a is supplied to the upper surface of the block layer 50a.
Further, as shown in FIG. 5C, the electrode 6 is placed on the upper surface of the second layer conductive paste.
Thereafter, in the case of phenol resin, the heat treatment is performed at a temperature of about 150 [° C.], whereby the two layers of the conductive paste are solidified to become current collectors 181a and 182a with the block layer 50a interposed therebetween, and the electrode 6 is stored in the reservoir. The component of the concave container 2 in which the electrode 6 is fixed by the current collector 181a, the block layer 50a, and the current collector 182a is completed.
In addition, you may make it perform the heat processing for heat-solidifying two layers of electrically conductive paste combining the concave container 2 and the sealing board 3 together.

Next, as shown in FIG. 6A, the separator 7 is placed on the electrode 6, and the electrolyte is supplied into the recess 13, so that the electrode 6 and the separator 7 are impregnated with the electrolyte.
Then, as shown in FIG. 6B, the parts on the sealing plate 3 side described in FIG. 3 are placed on the opening of the concave portion 13 so that the electrode 5 is on the concave portion 13 side. The electric double layer capacitor 1 is completed by brazing the metal layer 15 and the bonding metal layer 8 on the concave container 2 side.

Even when the thickness of the conductive paste is small, the electric resistance varies due to the difference or distribution of the thickness of the conductive paste.
Therefore, when applying the conductive paste, it is important to apply the conductive paste to a uniform thickness with the predetermined thickness set as described above. The current collectors 181a, 182a having an electronic conductive network by polymerizing the main component of the curing component and the solidification accelerator contained in the paste by a chemical reaction by heating after coating, and by contacting carbons with each other. 181b and 182b are formed.

At that time, an organic solvent may be added for the purpose of lowering the viscosity of the conductive paste, and when the solvent is vaporized, bubbles may be formed to form small diameter communication holes (holes) having a diameter of about several μm. . In addition, the above-described small-diameter communication holes may also be formed by gas components in the atmosphere entrained during application of the conductive paste.
Even in the case where such a hole or hole is formed in the conductive paste, in this embodiment, the block layers 50a and 50b are formed between the two conductive paste layers. , 15 is not contacted.

In addition, although it described above about the case where it cuts after forming a plurality of parts (sealing plate 3, metal layer 15, current collector 181b, block layer 50b, current collector 182b, electrode 5) on the side of sealing plate 3 which are mutually continuous, Similarly, after forming the continuous body of the concave container 2 in which the electrode 6 is fixed by the current collector 182a, the block layer 50a, and the current collector 181a, the parts 6 on each concave container 2 side (state of FIG. 5C) are formed. You may make it cut | disconnect.
Further, a separator 7 is disposed on each of the parts on the side of each concave container 2 before cutting and impregnated with an electrolyte, and a part on the side of the sealing plate 3 before cutting is covered thereon, and the metal layer 15 on the side of the sealing plate 3 A continuous pair of a plurality of electric double layer capacitors 1 may be formed by brazing the bonding metal layer 8 on the concave container 2 side, and then cut into individual electric double layer capacitors 1.

As described above, in the electric double layer capacitor 1 according to the present embodiment, the case where the current collectors 181a and 181b are formed by applying the conductive paste to the entire surfaces of the storage part 17 and the storage part 310 has been described. The following modifications may be adopted for the shape, the shape of the application surface, the application state, and the like.
Hereinafter, each modification on the concave container 2 side will be described with reference to FIG. 7, and each modification on the sealing plate 3 side will be described with reference to FIGS. 8 and 9. The electric double layer capacitor 1 can be configured by combining any one form of 2 and any one form of the sealing plate 3.

FIG. 7 shows a modification of the shape of the concave container 2 on the concave container 2 side.
The modification shown in FIG. 7A is an example in which the entire lower part of the recess 13 is used as a storage section without forming a step (storage section 17) in the recess 13.
In this modification, the step portion for the storage portion 17 is not required, and the area of the bottom of the concave portion 13 can be increased, so that the electrode 6 can be enlarged. Further, when the electrode 6 having the same size as that of the embodiment described is used, the electric double layer capacitor 1 can be relatively downsized.
Also for the concave container 2 shown in FIG. 7 (a), the current collector is composed of two layers of a current collector 181a and a current collector 182a, and a block layer 50a is disposed between the two layers, so that the electrolyte Is shut off.

In the modification shown in FIG. 7B, the concave container 2 having the same shape as in FIG. 7A is used, but the conductive paste is applied to the entire bottom surface and side surfaces of the recess 13 (the meniscus 192a portion in FIG. 7A). In this example, the current collector 181a is formed by applying the conductive paste only to the region (bottom surface) corresponding to the region where the surface electrode 6 is installed.
In this case, the conductive paste sandwiched between the bottom surface of the concave container 2 and the block layer 50a has a meniscus 191a formed on the periphery thereof, as described with reference to FIG. can do. Since the spread of the conductive paste is avoided, it is not necessary to increase the viscosity of the conductive paste compared to other cases, and it is possible to use a conductive paste having the same viscosity as other portions.

FIG. 7C shows the internal structure of the electric double layer capacitor 1 in which the electrodes 6 and 5 are arranged above and below the separator 7 in the embodiment described in FIG. 6 and 5 are arranged on the bottom surface of the concave container 2 side by side.
FIG. 7C is a side cross-sectional view of the electric double layer capacitor 1. The same components as those in the first embodiment are denoted by the same reference numerals, and description thereof is omitted.
A protrusion 33 that bisects the bottom surface is formed on the bottom surface of the recess 13. Then, on the bottom surface of the concave portion 13, two storage portions 17 a and 17 b that are reservoir portions for storing the conductive paste before solidification are formed by the protrusion 33.
In the reservoirs 17a and 17b, the conductive paste solidified with the block layers 50a and 50b interposed therebetween becomes current collectors 181a, 182a, 181b, and 182b, respectively. The conductive paste and block layers 50a and 50b used are the same as those in the first embodiment.

The depths of the storage portions 17a and 17b are such that the conductive paste is stored, and the inner periphery of the storage portions 17a and 17b is set to be larger than the outer periphery of the electrodes 5 and 6 by the meniscus of the conductive paste.
Metal layers 11a and 11b are formed on the bottom surfaces of the reservoirs 17a and 17b, respectively. The manufacturing method of the metal layers 11a and 11b is the same as that of the metal layer 11 in the above-described embodiment.
The reservoirs 17 a and 17 b are electrically connected to the terminals 10 and 12 by through electrodes 21 and 22 formed at the bottom of the concave container 2, respectively. The through electrodes 21 and 22 are reliably joined by the intermediate electrode 28.

In the storage portions 17a and 17b, layers of current collectors 181a and 181b obtained by solidifying the conductive paste are formed on the upper surfaces of the metal layers 11a and 11b, respectively, and further, the block layers 50a, 50b, Current collectors 182a and 182b are formed, and electrodes 5 and 6 are provided thereon.
In addition, although the metal layers 11a and 11b are formed in the minimum necessary area, you may form in the whole bottom face of the storage parts 17a and 17b.

The electrodes 5 and 6 have a rectangular parallelepiped shape and are made of the same material as the electrodes 5 and 6 of the first embodiment. The electrodes 5 and 6 may have other shapes such as a cylindrical shape.
In the modification of FIG. 7C, since the electrodes 5 and 6 are formed symmetrically, any of them may be a positive electrode.
Further, the electrodes 5 and 6 face each other at the upper part of the protruding portion 33, and a separator 7 for preventing a short circuit is disposed between the electrodes 5 and 6. The material of the separator 7 is the same as that of the first embodiment. Note that when the solid electrolyte is used, the separator 7 is not necessary.

The recess 13 is filled with an electrolyte, and an impregnation member (not shown) impregnated with the electrolyte is provided between the upper surface of the electrodes 5 and 6 and the lower surface of the sealing plate 3 (the surface of the metal layer 15). Is installed.
The impregnated member is formed in a sponge shape from a glass material, a resin wick, or the like, and has elasticity and liquid replacement properties. Due to the liquid replenishment property of the impregnated member, an effect of supplementing and applying the lost electrolyte solution can be obtained.
The impregnated member is pressed against the electrodes 5 and 6 and the separator 7. As a result, the impregnated member can hold the electrodes 5 and 6 and the separator 7 in a state where the electrodes 5 and 6 are in contact with the electrolyte.

The sealing plate 3 is formed of Kovar similarly to the embodiment, and the metal layer 15 is formed by nickel plating over the entire surface.
For example, the sealing plate 3 may be formed of aluminum, and an insulating layer made of alumina may be formed on the lower surface by thermal oxidation treatment. Thereby, even when the electrodes 5 and 6 are in contact with the lower surface of the sealing plate 3 due to impact or the like, a short circuit can be prevented.
The concave container 2 is formed by laminating sheet materials 41 to 45 made of green sheets, as in the first embodiment.
Through holes for forming the through electrodes 21 and 22 are formed in the sheet materials 41 and 42, and openings corresponding to the recesses 13 are formed in the sheet materials 43 to 45. In the sheet material 43, the portion that becomes the protrusion 33 remains without being pulled out.

FIG. 8 shows a modification regarding the shape of the sealing plate 3. FIG. 8 shows a state in which the electrode 5 faces downward in accordance with FIG. 2 showing the cross section of the electric double layer capacitor 1, but a two-layer conductive paste sandwiching the block layer 50 b between the sealing plate 3 and When the electrode 5 is fixed, the electrode 5 is formed on the upper side as described in FIG.
Further, each sealing plate 3 in FIGS. 8 and 9 (described later) has a surface brazed to the concave container 2 (surface of the metal layer 15 in the outer peripheral portion) and a surface of the electrode 5 opposite to the current collector 18b. Since the distance from the (open surface) is different, the depth of the concave portion 13 in the concave container 2 to be used (the concave container 2 in the embodiment and each modification) is adjusted according to the distance in each modification.

  Also in the modified example of the sealing plate 3, the sealing plate 3 and the electrode 5 are fixed by current collectors 181b and 182b sandwiching the block layer 50b, as in the embodiment described. Similarly to the embodiment, the block layer 50b blocks the electrolyte from passing through the holes and holes formed in the current collectors 181b and 182b.

The sealing plate 3 in the described embodiment is formed by curving the entire center portion of the board surface by press working. However, in the modification shown in FIG. 8A, the electric double layer capacitor 1 on the side where the electrode 5 is not attached. The surface on the outer peripheral surface side) remains flat, and a concave portion is formed only on the side to which the electrode 5 is attached to form the storage portion 310. The formation of the concave portion can be performed by pressing, etching, laser processing, cutting, or the like.
According to this modification, the outer surface of the electric double layer capacitor 1 on the sealing plate 3 side can be planar. By forming the storage portion 310 by the concave portion, it is possible to obtain effects such as positioning of the block layer 50b by the meniscus 192b as in the embodiment.

FIG. 8B shows a region where the electrode 5 is installed in the same manner as in the example of FIG. 7B, instead of using the flat sealing plate 3 and applying the conductive paste to the entire bottom surface of the sealing plate 3. This is an example in which the current collector 181b is formed by applying a conductive paste only in a region corresponding to the above. Also in the case of this modification, it is preferable to increase the viscosity of the conductive paste as in the case of FIG.
In the case of this modification as well, in the same way as in the case of FIG. 7B, the meniscus 192b can avoid excessive spreading of the conductive paste without increasing the viscosity of the conductive paste.

FIG. 8C shows a case where a recess having a shallower depth than that of the modification of FIG. In this case, the depth of the recess is shallower than the thickness of applying the conductive paste. For this reason, it is possible to prevent the conductive paste from being applied largely out of the position corresponding to the electrode 5 or protruding.
In this modified example, since the thickness of the conductive paste is larger than the depth of the recess, the peripheral surface of the conductive paste is not a concave meniscus 191b, but a convex curved surface is formed by surface tension. This convex curved surface is the same as in the case of the conductive paste (current collector 182b) that fixes the block layer 50b and the electrode 5 together.

In FIG. 8D, the storage portion 310 is formed by a concave portion whose entire plate is curved outward (one side) by pressing as in the case of the sealing plate 3 described in the embodiment. The dent 310 is formed deeper than the embodiment. The first layer of conductive paste is applied to the entire side surface of the reservoir 310, so that the current collector 181b is also formed on the entire side surface.
Note that the entire electrode 5 may be accommodated in the reservoir 310 by making the depth of the reservoir 310 deeper than that of the modified example of FIG.
According to the modified example of FIG. 8D and the modified example, the thickness of the concave container 2 can be reduced, and the production efficiency can be increased by reducing the number of sheets 41 to 41 stacked.

FIG. 8 (e) shows the sealing plate 3 formed with a two-stage dent due to bending, in the same manner as the concave container 2 in the embodiment is a two-stage dent of the recess 13 and the reservoir 17. . Then, the first layer of conductive paste is applied in the second dent formed in the center.
According to this modified example, the step portion formed by the first step dent and the second step dent acts as a spring to absorb the increase in internal pressure. The effect of can be obtained.

FIG. 9 shows a modification regarding the sealing plate 3 having springiness. FIG. 9 also shows a state in which the electrode 5 faces downward in accordance with FIG. 2 showing the cross section of the electric double layer capacitor 1, as in FIG. 8, but a conductive paste is applied to the sealing plate 3 to apply the electrode 5. Is fixed with the electrode 5 facing upward as described with reference to FIG.
Also in the modified example of the sealing plate 3, the sealing plate 3 and the electrode 5 are fixed by current collectors 181b and 182b sandwiching the block layer 50b, as in the embodiment described. Similarly to the embodiment, the block layer 50b blocks the electrolyte from passing through the holes and holes formed in the current collectors 181b and 182b.

As shown in FIGS. 9A and 9B, the sealing plate 3 includes an outer peripheral flat plate portion 3a, an annular groove portion 3b, and a central flat plate portion 3c.
The outer peripheral flat plate portion 3 a is an outer peripheral portion that is brazed to the concave container 2.
The central flat plate portion 3c is a flat plate portion on which the two layers of current collectors 181b and 182b and the electrode 5 are disposed with the block layer 50b interposed therebetween, and Rs are formed at four corners corresponding to the shape of the electrode 5. It is configured in a rectangular shape.
The annular groove portion 3b is a rectangular annular groove having R formed at four corners formed continuously with the outer peripheral flat plate portion 3a, and a central flat plate portion 3c is formed continuously with the annular groove portion 3b. . The entire surface of the annular groove 3b is curved, and an annular groove is formed when one surface is recessed, and a side cross section is formed in a bellows shape by forming a convex surface on the opposite side.

As shown in FIG. 9, the annular groove portion 3 b has the outer side of the cross section continuing to the outer peripheral flat plate portion 3 a and the inner side continuing to the central flat plate portion 3 c. That is, the annular groove 3b continuously connects the inner periphery of the outer peripheral flat plate portion 3a and the outer periphery of the central flat plate portion 3c.
The length (depth) of both side surfaces constituting the groove side is formed longer on the inner side than on the outer side, so that the outer peripheral plate portion 3a and the central flat plate portion 3c are not the same plane but different planes. It is supposed to be located.
It should be noted that the depth (length) of both side surfaces constituting the groove of the annular groove portion 3b may be made uniform so that the outer peripheral flat plate portion 3a and the central flat plate portion 3c are positioned on the same plane, You may make it comprise so that the outer side may become long rather than.
The sealing plate 3 in this modification is formed by pressing a plate material that is a raw material (described later).

In the modification shown in FIG. 9A, the metal layer 15 is formed on the opposite side of the formed annular groove, and the recess formed by the inner side surface of the annular groove portion 3b and the central flat plate portion 3c is used as a reservoir for the conductive paste. In the same manner as in the embodiment described in FIG. 2 and the modifications described in FIGS. 8A and 8C, the conductive paste applied as the current collector 18 and the arrangement of the electrodes 5 are used. Similar effects can be obtained.
In the example of FIG. 9A, the outer peripheral surface of the first layer of conductive paste shows the case where the meniscus 192b is formed by the surface tension with the inner side surface of the annular groove 3b. As in the modification shown in d), the outer peripheral surface is coated with the conductive paste on the entire inner side surface of the annular groove 3b (upper part (lower side of the drawing) than the example of FIG. 9A). May be.

  In the modification shown in FIG. 9B, the metal layer 15 is formed on the surface opposite to that in FIG. 9A, that is, on the side where the groove is formed by the formed annular groove 3b. Similar to the modification described in b), the first layer of conductive paste is applied to the central flat plate portion 3c, and the block layer 50b, the second layer of conductive paste, and the electrode 5 are disposed thereon.

According to the sealing plate 3 of the present modified example, the annular groove 3b extending in both the outer peripheral flat plate portion 3a and the central flat plate portion 3c is formed, so that the annular groove portion 3b functions as a spring structure, and the concave container 2 The pressure increase in the electric double layer capacitor 1 sealed with the sealing plate 3 can be absorbed, or when the increased pressure drops after reflow, the original state can be restored.
Thus, by adopting the spring structure by the annular groove 3b, it becomes possible to use a low boiling point solvent for the electrolyte and to manufacture the electric double layer capacitor 1 having a high withstand voltage.

That is, in the conventional electric double layer capacitor 1, in the case of using solder not containing lead in reflow for connecting the concave container 2 and the sealing plate 3, it is necessary to heat to about 260 ° C. It is necessary to use an electrolyte that does not exceed the limit, and the selection range of the electrolyte has been narrowed.
Further, when a voltage higher than the withstand voltage of the electrolyte is applied, bubbles may be generated due to decomposition of the electrolyte impregnated in the electrodes 5 and 6, and the electrodes 5 and 6 may expand due to the bubbles. In particular, when the withstand voltage of the electric double layer capacitor 1 is changed from 2.6 V to 3.3 V, the possibility that the electrodes 5 and 6 expand is high.
Furthermore, in the case of using an expandable electrode that expands when the electrode is impregnated with an electrolytic solution, depending on the type of the binder used for the electrode component and its blending amount, and the selection of the conductivity imparting material, There is also a possibility that the expansion of the electrode is excessively expanded.
With respect to such a problem, by using the sealing plate 3 adopting the spring structure by the annular groove portion 3b in the present modification, the electrode 5 which is intended to expand while absorbing the pressure increase in the electric double layer capacitor 1 is absorbed. , 6 can be used, a low boiling point solvent can be used for the electrolyte, and the pressure resistance can be increased. Further, a product with a high yield can be manufactured by expanding the electrodes 5 and 6.

  Here, it is preferable to use an aprotic polar solvent as an electrolyte (low boiling point solvent) that can be used by adopting the sealing plate 3 according to this modification, and among them, a chain ester, a chain ether, a glycol ether, among others. A chain carbonate is more preferable, and a chain ester and a chain carbonate are particularly preferable.

Examples of the chain ester include methyl formate (HCOOCH ₃ , MP: −99.8 ° C., BP: 31.8 ° C.), ethyl formate (HCOOC ₂ H ₅ , MP: −80.5 ° C., BP: 54. 3 ° C.), propyl formate (HCOOC ₃ H ₇ , MP: −92.9 ° C., BP: 81.3 ° C.), n-butyl formate (HCOO (CH ₂ ) ₃ CH ₃ , MP: −90 ° C., BP: 106 8 ° C.), isobutyl formate (HCOO (CH ₂ ) CH (CH ₃ ) ₂ , MP: −95 ° C., BP: 98 ° C.), amyl formate (HCOO (CH ₂ ) ₄ CH ₃ , MP: −73.5 ° C, BP: 130 ° C, formic acid ester, methyl acetate (H ₃ CCOOCH ₃ , MP: -98.5 ° C, BP: 57.2 ° C), ethyl acetate (H3CCOOC ₂ H ₅ , MP: -82.4) ° C, BP: 77.1 ° C), acetic acid-n-propyl (H ₃ CCOO (CH ₂ ) ₂ CH ₃ , MP: −92.5 ° C., BP: 101.6 ° C., isopropyl acetate (H ₃ CCOO (CH) (CH ₃ ) ₂ , MP: −69.3 ° C., BP : 89 ° C.), n-butyl acetate (H ₃ CCOO (CH ₂ ) ₃ CH ₃ , MP: −76.8 ° C., BP: 126.5 ° C.), isobutyl acetate (H ₃ CCOO (CH ₂ ) CH ( CH ₃ ) ₂ , MP: −98.9 ° C., BP: 118.3 ° C., dibutyl acetate (H ₃ CCOO (CH) (CH ₃ ) (CH ₂ CH ₃ ), MP: −99 ° C., BP : 112.5 ° C), acetic acid-n-amyl (H ₃ CCOO (CH ₂ ) ₄ (CH ₃ ), MP: -75 ° C, BP: 147.6 ° C), isoamyl acetate (H ₃ CCOO (CH ₂ )) _{2 (CH) (CH 3)} 2, MP: -78.5 ℃, BP: 142.5 ℃), acetic Mechiruisoami _{(H 3 CCOO (CH 2)} (CH 3) (CH 2) (CH) (CH 3) 2, MP: -63.8 ℃, BP: 146.3 ℃), acetic second hexyl (H ₃ CCOO ( CH) (CH ₃ ) (CH ₂ ) ₃ (CH ₃ ), MP: -63.8 ° C., BP: 146.3 ° C.) and other acetates, methyl propionate (H ₃ CCH ₂ COO (CH ₃ )), MP: −87 ° C., BP: 79.7 ° C.), ethyl propionate (H ₃ CCH ₂ COO (C ₂ H ₅ ), MP: −73.9 ° C., BP: 99.1 ° C.), propionic acid-n -Butyl (H ₃ CCH ₂ COO (CH ₂ ) ₃ CH ₃ , MP: -89.55 ° C., BP: 145.4 ° C.), isoamyl propionate (H ₃ CCH ₂ COO (CH ₂ ) ₂ CH (CH ₃ ) ₂ , MP: -73 ° C, BP: 160.3 ° C), etc. (H ₃ C (CH ₂ ) ₂ COO (CH ₃ ), MP: −95 ° C., BP: 102.3 ° C.), ethyl butyrate (H ₃ C (CH ₂ ) ₂ COO (CH ₂ ) (CH ₃ ) , MP: −93.3 ° C., BP: 121.3 ° C.), n-butyl butyrate (H ₃ C (CH ₂ ) ₂ COO (CH ₂ ) ₃ (CH ₃ ), MP: −91.5 ° C. BP: 166.4 ° C.), isoamyl butyrate (H ₃ C (CH ₂ ) ₂ COO (CH ₂ ) ₂ (CH) (CH ₃ ) ₂ , MP: −73.2 ° C., BP: 184.8 ° C.), etc. Aliphatic monocarboxylic acid esters such as butyric acid esters. As the chain carbonate, diethyl carbonate (H ₅ C ₂ OCOOC ₂ H ₅ , MP: −43 ° C., BP: 127 ° C.), ethyl methyl carbonate (H ₅ C ₂ OCOOCH ₃ , MP: −55 ° C., BP: 108 ° C) and the like.

On the other hand, as a material for forming the sealing plate 3 of this modification having a spring structure, as a corrosion-resistant alloy, SPRON (registered trademark), HASTELLOY (registered trademark), Elgiloy (registered trademark), Inconel Corrosion resistant alloys containing 32.5 wt% or more of (Inconel: registered trademark) and NI (nickel) can be used.
Sprone is a cobalt-nickel alloy, Hastelloy is an alloy that has increased corrosion resistance and heat resistance by adding a large amount of molybdenum and chromium to the nickel base (50Ni-Mo-Cr-Fe), and Elgiloy is an alloy containing cobalt, chromium, iron, and nickel Inconel is a nickel-based alloy such as iron, chromium, niobium, molybdenum (72Ni-15Cr-Fe, etc.).

  Also, as Fe-Ni alloys, 42-alloy (Fe-42Ni), Kovar (Fe-29Ni-17Co), Invar (Fe-36Ni), Elinvar (alloy of 36% nickel, 52% iron, 12% cobalt) An Fe—Ni alloy containing 29 wt% or more of NI (nickel) can be used.

Furthermore, stainless steel having corrosion resistance can be used as the material of the sealing plate 3, and in particular, austenitic stainless steel such as SUS301 is preferable because it has spring properties.
Austenitic stainless steel can be brazed directly to the bonding metal layer 8, but the adhesive strength when brazed directly is lower than that of brazing with the metal layer 15. For this reason, even when austenitic stainless steel is used for the sealing plate 3, the metal layer 15 is preferably plated.
By disposing the metal layer 15 on the sealing plate 3 formed of austenitic stainless steel, the brazing strength is increased and the block layer 50b prevents the electrolyte from contacting the metal layer 15.

  As for the material of the sealing plate 3 in the present modification described above (including the modification of FIG. 8E), all are suitable as materials having spring properties, but in particular, spron, invar, elinvar, austenite series. Stainless steel is preferable because of its excellent spring property.

Next, a modification of the concave container 2 with respect to the through electrodes 21 and 22 will be described with reference to FIG.
In the modification shown in FIG. 10A, the through electrodes 21 and 22 are not provided, and the electrodes 5 and 6 are connected to the terminals 10 and 12 by wiring formed on the side surface of the concave container 2. Other configurations are the same as those of the above-described embodiment.
The metal layer 11 penetrates from the bottom surface of the storage portion 17 to the outside of the concave container 2 along the surface of the sheet material 42, passes through the side surface of the concave container 2, and is electrically connected to the terminal 12 formed on the bottom surface of the concave container 2. Connected to.

The metal layer 11 is formed in the minimum necessary size on the bottom surface of the storage unit 17, but may be formed on the entire bottom surface. The metal layer 9 is bonded to the bonding metal layer 8 at the upper end surface of the concave container 2, and is electrically connected to the terminal 10 formed on the bottom surface of the concave container 2 through the side surface of the concave container 2.
On the side surface of the concave container 2, auxiliary electrodes are provided on the upper surfaces of the sheet materials 41 to 44 so that the electrical connection on the side surface is more reliable. Thus, the concave container 2 can also be configured in a manner that does not use a through electrode.

FIG. 10B shows an example in which the through electrode is formed of a conductive paste. When a through hole extending from the bottom surface of the storage portion 17 to the metal layer 11 is formed in the sheet material 42 and a conductive paste is injected into the storage portion 17, the conductive paste enters the through hole and solidifies. It is formed.
Further, by reducing the pressure after injecting the conductive paste, bubbles entrained together with the paste at the position of the through electrode 61 can be removed.
Since the current collector 181a and the through electrode 61 are integrally formed, the electrode 6 is electrically connected to the terminal 12 via the current collector 182a, the block layer 50a, the current collector 181a, the through electrode 61, and the metal layer 11. Connect to.
In this example, the bonding metal layer 8 and the terminal 10 are electrically connected by the through electrode 21.
10B, the current collector 181a and the metal layer 11 are electrically connected by the through electrode 61, and the bonding metal layer 8 and the terminal 10 are not the through electrode 21, but the through electrode 21. As in a), the metal layer 9 may be electrically connected.

Next, the modified example regarding the manufacturing method of the concave container 2 and the sealing board 3 is demonstrated.
That is, in the sealing plate (FIG. 3) and the concave container 2 (FIGS. 4 and 5) according to the embodiment described above, the first layer of conductive paste and block to be the current collectors 181 a and 181 b are applied to the concave container 2 and the sealing plate 3. The case where the layers 50a and 50b, the second layer conductive paste to be the current collectors 182a and 182b, and the electrodes 5 and 6 are arranged in this order has been described.
On the other hand, a preassembled unit composed of the block layers 50a and 50b, the current collectors 182a and 182b, and the electrodes 5 and 6 is formed in advance, and this preassembled unit is formed into the concave container 2 with the first layer of conductive paste. Alternatively, it may be fixed to the sealing plate 3.

FIG. 11 shows each process of the manufacturing method of a pre-assembly unit, FIG. 11 (a)-(d) shows sectional drawing in each process, (e) represents the perspective view after a cutting | disconnection.
First, as shown in FIG. 11A, the aluminum plates (foil) 51a and 51b before cutting are allowed to stand.
In addition, although the aluminum plate is a thing before a cutting | disconnection, the code | symbol corresponding to the member at the time of completion of the pre-assembled units 600 and 500 is attached | subjected (the same is true hereafter). Further, since the manufacturing process is the same for both the pre-assembled unit 600 for the concave container 2 and the pre-assembled unit 500 for the sealing plate 3, the description will be made collectively by putting both symbols together.

Next, as shown in FIG. 11B, the block layers 50a and 50b are formed by pre-coating the carbon layers 52a and 52b on the entire surfaces of the aluminum plates 51a and 51b that have been allowed to stand.
Methods for pre-coating the block layers 50a and 50b include spin coating, doctor blade method, reverse roll method, direct roll method, dipping method, squeeze method, extrusion method, curtain method, bar method, knife method and the like. However, the present invention is not limited to these examples.

Next, as shown in FIG. 11C, a conductive paste to be the second-layer current collectors 182a and 182b is applied to the entire upper surface of the block layers 50a and 50b (the upper portions of the carbon layers 52a and 52b).
Next, as shown in FIG. 11 (d), an electrode active material that is mainly composed of activated carbon and becomes electrodes 6 and 5 is applied onto the conductive paste, and then the whole is heat-treated at a temperature of about 150 ° C. Then, the conductive paste is solidified and the block layers 50a and 50b and the electrodes 6 and 5 are fixed to form a pre-assembled unit group.

  The preassembled unit group for the concave container 2 and the preassembled unit 500 for the sealing plate 3 are formed as shown in FIG. To do.

When the pre-assembled unit 600 formed in this way is used, the pre-assembled unit 600 is placed on the block layer 50a on the first conductive paste (see FIG. 4A) applied to the reservoir 17 of the concave container. Place so that is on the bottom.
Further, the pre-assembled unit 500 is arranged on the first conductive paste (see FIG. 3B) applied on the sealing plate 3 so that the block layer 50b is on the bottom.
Thereafter, the first layer of conductive paste is solidified by heat treatment of the concave container 2 and the sealing plate 3 in which the pre-assemble units 600 and 500 are arranged, and the pre-assemble units 600 and 500 are assembled by the current collectors 181b and 181a after solidification. The concave container 2 and the sealing plate 3 are fixed.

Thereafter, as described with reference to FIGS. 6A and 6B, after the separator 7 is placed and the electrolyte is supplied, the metal layer 15 on the sealing plate 3 side and the bonding metal layer 8 on the concave container 2 side are soldered together. As a result, the electric double layer capacitor 1 is completed.
In this way, as described in the present modification, a group of pre-assembled units is formed and a plurality of pre-assembled units 600 and 500 are formed by punching, so that they can be efficiently manufactured.
Further, the number of manufacturing steps is reduced because it is only necessary to arrange the pre-assembled units 600 and 500 on the first layer of conductive paste, rather than stacking multiple layers of conductive paste on the concave container 2 or the sealing plate 3. be able to.

Next, modified examples of the current collectors 181a, 182a, 181b, and 182b and the block layers 50a and 50b will be described with reference to FIGS. 12 (a) and 12 (b), as in FIG. 1, the right side represents the configuration on the concave container 2 side, and the left side represents the configuration on the sealing plate 3 side, with the one-dot chain line in the middle.
FIG. 12A illustrates a modification of the current collectors 181a, 182a, 181b, and 182b.
In the described embodiment or modification, the first-layer current collectors 181a and 181b and the second-layer current collectors 182a and 182b are completely separated by the block layers 50a and 50b (in contact with each other). No state).
On the other hand, in the present modification shown in FIG. 12A, the first-layer current collectors 181a and 181b and the second-layer current collectors 182a and 182b are arranged on the outer peripheral side of the block layers 50a and 50b. The entire circumference or at least part of the circumference is connected (continuous state). Thereby, the block layers 50a and 50b are buried in the portion where the current collector is connected.

In this modification, the current collectors 181a, 182a, 181b, and 182b are continuous on the outer periphery of the block layers 50a and 50b, but the area in a cross section parallel to the block layers 50a and 50b is continuous on the entire periphery. In this case, the area is slightly smaller than the area of the entire region where the electrodes 6 and 5 are opposed to the metal layer 11 and the metal layer 15. For this reason, the amount of communication holes from the electrodes 6 and 5 to the metal layers 11 and 15 formed on the outer periphery of the block layers 50a and 50b is sufficiently smaller than that in the case where the block layers 50a and 50b are not present.
In addition, since the first layer of current collectors 181a and 181b and the second layer of current collectors 182a and 182b are applied separately, the surface of the communication holes and holes generated by the first application Is often blocked by the next application.
Furthermore, after the first-layer current collectors 181a and 181b are heated and solidified from the conductive pace, the surface of the hole or the like can be more reliably closed by applying the second-layer conductive paste.
In addition, as described with reference to FIG. 11, a pre-assembled unit composed of previously formed block layers 50 a and 50 b, current collectors 182 a and 182 b, and electrodes 5 and 6 is applied to the concave container 2 and the sealing plate 3 to form one layer. When disposed on the conductive paste of the eyes, the current collectors 181a, 181b and the current collectors 182a, 182b may be continuous over the entire outer periphery or at least a part of the block layers 50a, 50b. Even in this case, since the current collectors 182a and 182b of the pre-assembly unit are already heated and solidified, even if a hole or the like is formed on the outer peripheral surface, the first-layer conductive paste that becomes the current collectors 181a and 181b It will be blocked by.
Therefore, as shown in FIG. 12A, the current collectors 181a and 181b in the layer and the current collectors 182a and 182b in the second layer are connected on the outer peripheral side of the block layers 50a and 50b (see FIG. Even when the block layers 50a and 50b are not present, the amount of the electrolytic solution reaching the metal layers 11 and 15 from the electrodes 6 and 5 can be sufficiently reduced even when the block layers 50a and 50b are not present. is there.

FIG. 12B shows a modification regarding the shapes of the block layers 50a and 50b.
In this modified example, as shown in FIG. 12B, the standing end portions 500a and 500b facing the side walls of the electrodes 6 and 5 are formed by standing the outer peripheral side end portions of the block layers 50a and 50b. Is formed. The height of the standing ends 500a and 500b is formed to be equal to or less than the same height as the surface of the electrodes 6 and 5 (surface opposite to the block layers 50a and 50b).
Further, the standing end portions 500a and 500b are preferably formed so as to face each other over the entire circumference of the electrodes 6 and 5, but only a part (for example, the four facing surfaces of the electrodes 6 and 5 face each other). 2 surfaces, any one surface, a part of each surface, etc.) may be formed to face each other.
The side walls of the electrodes 6 and 5 and the standing ends 500a and 500b of the block layers 50a and 50b are fixed by the conductors 182a and 182b by heating the conductive paste applied between them at a high temperature.
According to this modification, the electrodes 6 and 5 have a large current collection area by contacting the current collectors 182a and 182b not only on the surface facing the concave container 2 and the sealing plate 3, but also on the side surfaces. Therefore, the contact resistance can be reduced.

In the modification shown in FIG. 12B, the case where the current collectors 182a and 182b are disposed between the standing ends 500a and 500b of the block layers 50a and 50b and the electrodes 6 and 5 has been described. The current collectors 181a and 181b may be disposed between the outer side surfaces of the standing end portions 500a and 500b and the inner side surface portions formed on the concave container 2 and the sealing plate 3.
In this case, as the inner side surface portion of the concave container 2, the inner side wall portion of the recess portion 13 when the inner side wall portion of the storage portion 17 in FIG. 1 or the storage portion 17 shown in FIG. Section. In the case of the modification shown in FIG. 7C, the current collectors 181a and 181b may be disposed not only on the inner side wall portion of the recess 13 but also on both side surfaces of the separator 7. .
On the other hand, as the inner side surface portion of the sealing plate 3, the inner side wall surface (recessed portion is formed) of the storage portion 310 shown in FIG. 1 (c), FIG. 8 (a), (d), (e) and FIG. 9 (a). Applicable to the slope).

  12B and FIG. 12A are combined so that the current collectors 181a and 181b and the current collector 182a extend beyond the standing ends 100a and 500b of the block layers 50a and 50b. 182b may be configured to be at least partially continuous.

In the embodiment described above and each of the modifications described above, the case where one block layer 50a, 50b (with or without the carbon layers 52a, 52b) is provided has been described, but a plurality of blocks are provided. It may be.
In this case, the block layer may be bent one or more times to form a plurality of block layers continuous at the bent portion. For example, a five-layer block layer that is bent four times may be used.
By using the block layers 50a and 50b bent in this way, spring properties (cushion properties) can be provided.

Further, in the present embodiment and each modification described above, an electric double layer capacitor has been described as an example of an electrochemical cell constituting the electronic component. However, the electronic component is not limited to a lithium ion capacitor, a nonaqueous electrolyte battery, or the like. It is also possible to have a kind of electrochemical cell.
For example, an electrode sheet composed of silicon oxide activated by metallic lithium (50 wt%), a conductive additive (40 wt%), and a polyacrylic acid binder (20 wt%) is used as the negative electrode, and the positive electrode is used as the positive electrode. And an electrode sheet composed of an active material (85 wt%) having a spinel type crystal structure of lithium-manganese-oxygen, a conductive assistant (10 wt%), and a PTFE binder (5 wt%), A separator made of glass fiber and a battery composed of an electrolyte by dissolving 1M LiN (SO ₂ CF ₃ ) ₂ in PC (propylene carbonate) or EC (ethylene carbonate) are possible. Here, the size of the positive electrode and the negative electrode can be 1 mm long × 1.5 mm wide × 0.2 mm thick.
Furthermore, in addition to the positive electrode active material described above, LiFePO ₄ , Li ₄ Ti ₅ O ₁₂ , Li ₄ Mn ₅ O ₁₂ , LiCoO _2, etc. can also be used. Alternatively, Li—Si—O, Li—AL, or the like can be used as the negative electrode active material.
In addition, a lithium ion battery can be configured by using an electrolytic solution in which 1M LiBF ₄ is dissolved in PC. At this time, a conductive additive or a binder can be used in combination with each active material.

In this way, the present invention can be applied to various lithium ion capacitors (LIC) and lithium ion batteries (LIB). In all cases, aluminum is used for the positive electrode block layer 50a.
On the other hand, a material corresponding to the active material is used for the negative electrode block layer 50b. That is, as a material that does not react with both the electrolyte and the negative electrode side active material, for example, AL is used for an ion capacitor, Cu is used for a battery whose negative electrode active material is LiC ₆ , and SUS or Cu is used for a battery whose negative electrode active material is LiSiO _x. In a battery whose negative electrode active material is Li ₄ Ti ₅ O ₁₂ , AL, SUS, or Cu is used.

  In the embodiment described above, the block layer 50a is disposed between the current collector 181a obtained by solidifying the conductive paste as a two-layer structure and the current collector 182a, and between the current collector 181b and the current collector 182b. Since the block layer 50b is provided, the electrolyte impregnated in the electrodes 6 and 5 is blocked by the block layers 50a and 50b. Therefore, the amount of elution during use when the electrolyte contacts the metal layers 11 and 15 is minimized. Can be reduced.

DESCRIPTION OF SYMBOLS 1 Electric double layer capacitor 2 Concave container 3 Sealing plate 3a Outer peripheral flat plate part 3b Annular groove part 3c Central flat plate part 310 Reservoir part 5 Electrode 6 Electrode 7 Separator 8 Joining metal layer 9 Metal layer 10 Terminal 11 Metal layer 12 Terminal 13 Recess 15 Metal layer 17 Storage part 181a, 181b, 182a, 182b Current collector 50a, 50b Block layer 51a, 51b Aluminum layer 52a, 52b Carbon layer 191a, 191b, 192a, 192b Meniscus 21, 22 Through electrode 28 Intermediate electrode 41-45 Sheet material 61 Through electrode

Claims (4)

Consists of a concave container and a sealing plate, a container having a cavity,
A first metal layer formed on the bottom of the concave container in the cavity,
A first electrode disposed in the cavity;
A first current collector electrically connecting the first electrode to the first metal layer and disposing the first electrode on an inner bottom surface of the concave container;
A second metal layer formed on the cavity side of the sealing plate;
A second electrode disposed in the cavity at a predetermined distance from the first electrode;
A second current collector for electrically connecting the second electrode to the second metal layer and disposing the second electrode on the sealing plate;
An electrolyte impregnated in the first electrode and the second electrode,
At least one of the first current collector and the second current collector is formed of a resin having carbon as a conductive material, and the first layer current collector, the second layer current collector, and the first layer current collector. And a block layer sandwiched between the current collector and the second-layer current collector, having a conductivity, a blocking property for blocking the electrolyte, and an electrochemical resistance to the electrolyte ,
The sealing plate is composed of an outer peripheral flat plate portion connected to the concave container, a central flat plate portion, an annular groove portion that continuously connects an inner periphery of the outer peripheral flat plate portion and an outer periphery of the central flat plate portion,
The second metal layer, the second current collector, and the second electrode are disposed on the central flat plate portion ,
An electronic component characterized by that.   The electronic component according to claim 1, wherein the block layer includes an aluminum layer and a carbon layer formed on a surface on the first electrode side. The second metal layer, the second current collector, and the second electrode are disposed in a recess formed by the annular groove and the central flat plate. The electronic component according to claim 1 or 2 . An electronic component according to any one of claims of claims 1 to 3,
Power storage means for storing power in the electronic component;
With other electronic components that perform the specified function,
Power supply means for supplying power to the other electronic component using the stored charge;
An electronic device comprising:

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