Method and apparatus for producing a composite electrode

Abstract

To provide a composite electrode manufacturing method with high yield and material efficiency, and a composite electrode manufacturing apparatus.SOLUTION: There is provided a manufacturing method of a composite electrode including a substrate and an insulating fiber film provided on the substrate. The manufacturing method includes applying a primer solution to a strip-shaped substrate, and forming the insulating fiber film on the main surface of the substrate by ejecting a charged raw material liquid in a direction parallel to the main surface intersecting the side surface of the substrate and depositing it on the substrate.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] An embodiment of the present invention relates to a method and an apparatus for manufacturing a composite electrode. [Background technology]

[0002] There is an electrospinning apparatus that deposits fine fibers on the surface of a collector or a substrate by electrospinning (sometimes called electrospinning or electric-charge spinning) to form a fiber film. An example of an electrospinning apparatus is provided with an electrospinning head, which includes a head body and a nozzle protruding from the outer circumferential surface of the head body. In the electrospinning head, a storage cavity capable of storing the raw material liquid is formed inside the head body. In addition, a flow path (nozzle flow path) that communicates with the storage cavity is formed inside the nozzle, and an outlet of the flow path is formed at the end of the nozzle protruding from the head body. By applying a voltage between the nozzle (electrospinning head) and the collector or substrate, the raw material liquid is ejected from the outlet of the flow path toward the surface of the collector or substrate, and fibers are deposited on the surface of the collector or substrate.

[0003] Known applications of the fiber membrane thus formed include, for example, separation membranes that require electrical insulation, such as separators used in electricity storage devices such as lithium ion secondary batteries and electric double layer capacitors. In addition, due to the widespread use of portable electronic devices, there is a demand for miniaturization of electricity storage devices. In the electrospinning method, the fibers ejected toward the surface of the collector or substrate are deposited over a wide range of a certain extent or more. Therefore, when applying the membrane obtained by the electrospinning method to a small electricity storage device, further processing is required or material is wasted. Therefore, there is a demand for improvements in production efficiency and material efficiency in the formation of small-sized membranes. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2010-500717 [Patent Document 2] JP 2013-80828 A [Patent Document 3] JP 2013-251347 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the embodiments is to provide a method and apparatus for manufacturing a composite electrode with high yield and material efficiency. [Means for solving the problem]

[0006] According to an embodiment, a method for manufacturing a composite electrode including a substrate and an insulating fiber membrane provided on the substrate is provided. The method includes applying a primer solution to a strip-shaped substrate, and applying a charged raw material solution to the substrate in a direction parallel to a main surface intersecting with a side surface of the substrate. The material is sprayed toward one long side of the substrate, and toward the other long side of the substrate at a position shifted along the longitudinal direction of the substrate. and forming an insulating fibrous membrane on a major surface of the substrate by jetting and depositing the insulating fibrous membrane on the major surface of the substrate.

[0007] According to another embodiment, there is provided a manufacturing apparatus for a composite electrode, the manufacturing apparatus including a conveying mechanism for conveying a belt-shaped base material along a conveying path, a coater for applying a primer solution to the base material, and a nozzle for spraying a raw material liquid. Equipped The coating machine includes an electrospinning unit. To be transported A primer solution is applied to the substrate. Electrospinning unit The nozzle is the above conveying route The primer solution is applied by the above coater. Downstream from the position In The above transport route The raw material liquid is sprayed onto the substrate being transported. . At least one of the nozzles facing a side surface on one long side of the substrate and at least one of the nozzles facing a side surface on the other long side of the substrate are arranged to be offset from one another along the longitudinal direction of the substrate. The flow direction of the flow channel communicating with the nozzles is parallel to the main surface intersecting the side surface of the substrate. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a perspective view illustrating an example of a manufacturing apparatus for a composite electrode according to an embodiment. [Diagram 2]FIG. 2 is a schematic cross-sectional view showing an example of a coater included in the manufacturing apparatus for a composite electrode according to the embodiment. [Diagram 3] FIG. 11 is a schematic cross-sectional view showing another example of a coater included in the manufacturing apparatus for a composite electrode according to the embodiment. [Figure 4] FIG. 2 is a partially transparent view illustrating an example of an electrospinning machine included in the manufacturing apparatus for a composite electrode according to the embodiment. [Diagram 5] FIG. 13 is a perspective view illustrating another example of an electrospinning machine included in the manufacturing apparatus for a composite electrode according to the embodiment. [Figure 6] FIG. 4 is a schematic cross-sectional view showing an example of a drying step that may be included in the method for producing a composite electrode according to the embodiment. [Figure 7] FIG. 4 is a schematic cross-sectional view showing an example of rolling that may be included in the method for producing a composite electrode according to the embodiment. [Figure 8] FIG. 1 is a perspective view for illustrating the spread of fibers when a raw material liquid is ejected in a conventional electrospinning method. [Figure 9] FIG. 1 is a perspective view for illustrating the spread of fibers when a raw material liquid is ejected in a conventional electrospinning method. [Figure 10] FIG. 2 is a plan view illustrating an example of a component of an electrolytic capacitor body using a composite electrode according to an embodiment. [Figure 11] FIG. 11 is an enlarged view of part A shown in FIG. [Figure 12] FIG. 2 is a partially exploded perspective view illustrating an example of an electrolytic capacitor body including a composite electrode according to an embodiment. [Figure 13] FIG. 1 is a perspective view illustrating an example of an electrolytic capacitor including a composite electrode according to an embodiment. [Figure 14] FIG. 1 is a plan view illustrating an example of components of a conventional electrolytic capacitor body. [Figure 15] FIG. 1 is a partially exploded perspective view illustrating a schematic example of a conventional electrolytic capacitor body. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The manufacturing method according to the embodiment is a method for manufacturing a composite electrode including a band-shaped substrate and an insulating fibrous membrane provided on the substrate. The manufacturing method includes applying a primer solution to the band-shaped substrate and forming an insulating fibrous membrane on a main surface of the substrate. The insulating fibrous membrane is formed on the main surface of the substrate by ejecting a charged raw material solution in a direction parallel to the main surface intersecting with the side surface of the substrate and depositing the charged raw material solution on the substrate.

[0010] The manufacturing apparatus according to the embodiment is an apparatus for manufacturing the composite electrode, and is an apparatus for manufacturing the composite electrode by the manufacturing method. The manufacturing apparatus includes a conveying mechanism, a coater, and an electrospinning unit. The conveying mechanism conveys a band-shaped substrate along a conveying path. The coater coats the substrate with a primer solution at a first position on the conveying path. The electrospinning unit is provided at a second position downstream of the first position on the conveying path. The electrospinning unit is provided such that the flow direction of a flow path communicating with a nozzle for ejecting the raw material liquid is parallel to a main surface of the substrate that intersects with a side surface of the substrate.

[0011] Hereinafter, embodiments will be described with reference to the drawings.

[0012] 1 is a perspective view showing an example of a manufacturing apparatus for a composite electrode according to an embodiment. The manufacturing apparatus 1 shown in the figure includes a winder 20, a coater 30a, an electrospinning machine 40a including an electrospinning nozzle 412 as an electrospinning unit, a drying furnace 50, a press 60, a winder 70, and a plurality of guide rollers 90. In this manufacturing apparatus 1, a conveying mechanism is configured in which the unwinder 20, the winder 70, and the plurality of guide rollers 90 convey the substrate 8 along a conveying path 100.

[0013] The unwinder 20 includes a reel 21. The base material 8 is wound in a roll shape around the reel 21. In the unwinder 20, the reel 21 is rotated by driving a driving member (not shown) such as an electric motor. Due to the rotation, the base material 8 wound around the reel 21 is unwound. Then, the unwound base material 8 is paid out to the transport path 100.

[0014] The winding machine 70 includes a reel 71. In the winding machine 70, the reel 71 rotates by driving a driving member (not shown) such as an electric motor. As a result, the base material 8 transported along the transport path 100 is wound into a roll by the reel 71.

[0015] In the manufacturing apparatus 1, the reel 21 is rotated while the reel 71 is rotated at the same time, whereby the substrate 8 is transported from the unwinder 20 to the winder 70 along the transport path 100. Note that the number and arrangement of the guide rollers 90 that guide the substrate 8 from the unwinder 20 to the winder 70 are not limited to those shown in the figure. Also, the number and arrangement of the bends and fold-back portions in the transport path 100 from the unwinder 20 to the winder 70 are not limited to those shown in the figure.

[0016] 1 shows an example of a roll-to-roll type apparatus in which the substrate 8 unwound from the unwinder 20 passes continuously through each part of the manufacturing apparatus 1 on the conveying path 100 and is finally wound up by the winder 70, but the embodiment (both the manufacturing method and the manufacturing apparatus) are not limited to such a continuous type. For example, an insulating fiber film can be formed on the substrate 8 by a sheet-by-sheet type that will be specifically described downstream.

[0017] The substrate 8 has a band shape. The band shape of the substrate 8 has a short side width of, for example, 2 mm or more and 6 mm or less. The substrate 8 is preferably a conductive foil. The substrate 8 is more preferably a conductive foil having an oxide coating functioning as a dielectric layer chemically formed on its surface. In one example, the substrate 8 is an aluminum foil coated with an aluminum oxide coating. The substrate may have a thickness of, for example, 50 μm or more and 200 μm or less.

[0018] An applicator 30a is installed at a first position 3a on the transport path 100 of the substrate 8, downstream of the unwinder 20. The applicator 30a applies a primer solution 300 to the substrate 8.

[0019] In the illustrated example, a primer solution 300 is applied to the substrate 8 by a dip coating method at the first position 3a. Fig. 2 shows the primer treatment of the substrate 8 by such a dip coating method in more detail.

[0020] FIG. 2 is a schematic cross-sectional view showing in more detail the application of the primer solution 300 to the substrate 8 at the first position 3a in this embodiment. The coater 30a installed at the first position 3a includes a container 31. The container 31 defines a space through which the substrate 8 passes, and is capable of containing the primer solution 300. In the illustrated example, the coater 30a further includes a pair of metering rolls 32. At the first position 3a, a guide roller 90 is disposed so that the substrate 8 passes through the primer solution 300 once and then is lifted up from the primer solution 300. The guide roller 90 is disposed so that the substrate 8 lifted up from the primer solution 300 passes between the metering rolls 32.

[0021] At the first position 3a, the substrate 8 is immersed in the primer solution 300 while being transported along the transport path 100, so that the primer solution 300 is applied to the surface of the substrate 8, forming a primer coating 81 that covers the substrate 8. The substrate 8 coated with the primer coating 81 passes between a pair of metering rolls 32, whereby the excess primer solution 300 is removed, and a uniform primer coating 81 is formed.

[0022] The primer solution 300 contains, for example, one or more selected from the group consisting of ethylene glycol and γ-butyrolactone. In addition, an organic solvent that is widely used as a solvent for an electrolyte used in a capacitor or condenser may be used as the primer solution 300. Examples of such organic solvents include ethylene glycol monomethyl ether, glycerin, and N-ethylformamide.

[0023] The container 31 of the coater 30a is made of a material that is resistant to the primer solution 300, for example, a synthetic resin material.

[0024] In the manufacturing method and manufacturing apparatus according to the embodiment, instead of the above-mentioned dipping method, a spray method can be used to apply the primer solution 300 to the substrate 8. Fig. 3 shows the primer treatment of the substrate 8 by such a spray coating method.

[0025] 3 is a schematic cross-sectional view showing application of a primer solution 300 to a substrate 8 by a spray method. At the first position 3b, in addition to a guide roller 90 that defines a transport path 100 for the substrate 8, an applicator 30b is disposed that includes a sprayer equipped with a spray nozzle 33 that sprays the primer solution 300 toward the substrate 8 and a primer supply source 34.

[0026] The spray nozzle 33 is supplied with primer solution 300 from a primer supply source 34. The primer supply source 34 includes a primer solution storage tank 341, a primer supply drive unit 342, a primer supply adjustment unit 343, and a primer supply pipe 345. Each of the primer solution storage tank 341, the primer supply drive unit 342, the primer supply adjustment unit 343, and the primer supply pipe 345 is formed from a material that is resistant to the primer solution 300. The sprayer may further include a control unit (not shown) that controls the drive of the primer supply drive unit 342 and the operation of the primer supply adjustment unit 343.

[0027] At the first position 3b, the spray nozzle 33 sprays the primer solution 300 onto both the front and back principal surfaces of the substrate 8 being transported along the transport path 100, thereby coating the principal surfaces of the substrate 8 with a primer coating 81. In the illustrated example, the spray nozzle 33 is arranged so that one principal surface of the substrate 8 is coated with the primer coating 81 before the other principal surface is coated, but the arrangement of the spray nozzle 33 is not limited to the illustrated example. For example, the spray nozzle 33 may be arranged so that both sides of the substrate 8 are simultaneously exposed to a mist of the primer solution 300.

[0028] The number of spray nozzles 33 is not particularly limited, and one or more spray nozzles 33 may be provided on each side of the substrate 8. Alternatively, it is possible to provide a mechanism for changing the positional relationship between the spray nozzles 33 and the substrate 8 so that after the primer solution 300 is sprayed onto one main surface of the substrate 8 using one or more spray nozzles 33, the one or more spray nozzles 33 spray the primer solution 300 onto the other main surface of the substrate 8. Also, a configuration in which the primer solution 300 is sprayed onto the entire surface of the substrate 8, including the side surfaces in addition to the main surfaces, is desirable.

[0029] The spray nozzle 33 is preferably made of a material that is resistant to the primer solution 300, for example, stainless steel.

[0030] The form of the sprayer is not limited to a form equipped with the spray nozzle 33 shown in the figure, as long as it has a configuration for spraying the primer solution 300 onto the substrate 8.

[0031] The method of applying the primer solution 300 to the substrate 8 is not limited to the above-mentioned dipping method and spraying method.

[0032] In the transport path 100 of the substrate 8, an electrospinning machine 40a is provided at a second position 4a downstream of the first position 3a (or the first position 3b) where the primer solution 300 is applied to the substrate 8. The electrospinning machine 40a is provided with an electrospinning nozzle 412 with a nozzle facing the side surface of the substrate 8. At the second position 4a, the raw material liquid of the insulating fiber membrane of the composite electrode is ejected from the electrospinning nozzle 412 toward the side surface of the substrate 8 in a charged state and deposited on the substrate 8. The charged raw material liquid is ejected from the electrospinning nozzle nozzle installed so as to face the side surface of the substrate 8 and deposited on the substrate 8, whereby an insulating fiber membrane is formed on the main surface of the substrate 8.

[0033] The formation of an insulating fiber membrane by electrospinning will be described in detail with reference to Fig. 4. Fig. 4 is a partial perspective view showing an example of an electrospinning machine installed at the second position. In Fig. 4, the main surface of the substrate 8 is shown.

[0034] The electrospinning machine 40b shown in the figure includes an electrospinning head 41 and a raw material liquid supply source (supply unit) 42 as an electrospinning unit, and further includes a power source 43 and a control unit 44.

[0035] The electrospinning head 41 includes a head body 411 and an electrospinning nozzle 412. The electrospinning nozzle 412 is provided on the outer surface of the head body 411. Each of the head body 411 and the electrospinning nozzle 412 is formed from a conductive material.

[0036] The number of the electrospinning nozzles 412 is not particularly limited, and one or more electrospinning nozzles 412 may be provided. Each of the head body 411 and the electrospinning nozzle 412 is preferably made of a material having resistance to the raw material liquid described later, for example, stainless steel.

[0037] A storage cavity 415 is formed inside the head body 411. The electrospinning head 41 has the same number of flow paths (nozzle flow paths) 417 as the electrospinning nozzles 412, and each electrospinning nozzle 412 has a corresponding one of the flow paths 417 inside. One end of each of the flow paths 417 communicates with the storage cavity 415 and extends from the storage cavity 415 toward the outside of the head body 411. Each of the flow paths 417 has an outlet 418 formed at the end opposite to the storage cavity 415, and each of the flow paths 417 opens to the outside at the outlet 418. Each of the electrospinning nozzles 412 has a corresponding one of the flow paths 417 at the tip protruding from the head body 411.

[0038] The electrospinning nozzle 412 may be, for example, a needle-type nozzle. In the illustrated example, the electrospinning nozzle 412 includes a nozzle base 412a and a needle portion 412b. In the electrospinning nozzle 412, the nozzle base 412a is connected to the head body 411 and forms the root of the protruding portion from the head body 411. In the electrospinning nozzle 412, the needle portion 412b further protrudes from the nozzle base 412a to the outer periphery side of the electrospinning head 41 and forms the protruding end from the head body 411. An ejection port 418 is formed at the tip of the needle portion 412b. In addition, the outer diameter of the needle portion 412b is smaller than the outer diameter of the nozzle base 412a. The shape of the electrospinning nozzle 412 is not limited to the illustrated example.

[0039] The raw material liquid supply source 42 includes a raw material liquid storage section 421, a raw material liquid supply drive section 422, a raw material liquid supply adjustment section 423, and a raw material liquid supply pipe 425. Each of the raw material liquid storage section 421, the raw material liquid supply drive section 422, the raw material liquid supply adjustment section 423, and the raw material liquid supply pipe 425 has resistance to the raw material liquid, and in one example, each of the raw material liquid storage section 421 and the raw material liquid supply pipe 425 is made of an insulating material such as fluororesin.

[0040] The raw material liquid storage unit 421 is a tank or the like that stores the raw material liquid. The raw material liquid is a polymer material dissolved in a solvent. The polymer contained in the raw material liquid and the solvent that dissolves the polymer are appropriately determined according to the material type of the insulating fiber film to be formed on the substrate 8, etc.

[0041] The polymer material is not particularly limited and can be appropriately changed depending on the material of the insulating fiber membrane to be formed. In one example, one or more selected from the group consisting of polyamide and polyamide-imide can be used as the polymer material. Other examples of the polymer material that can be used include polypropylene, polyethylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, polycarbonate, nylon, and aramid.

[0042] The solvent used in the raw material liquid may be any solvent capable of dissolving the polymeric material. The solvent may be appropriately changed depending on the polymeric material to be dissolved. Examples of the solvent that may be used include water, methanol, ethanol, isopropyl alcohol, acetone, benzene, toluene, N-methyl-2-pyrrolidone (NMP), and dimethylacetamide (DMAc).

[0043] The raw material liquid supply pipe 425 connects between the raw material liquid storage unit 421 and the head body 411 of the electrospinning head 41. A flow path for the raw material liquid is formed inside the raw material liquid supply pipe 425. The raw material liquid supply pipe 425 is connected to the head body 411, and the storage cavity 415 communicates with the inside of the raw material liquid supply pipe 425.

[0044] The raw material liquid supply drive unit 422 is driven or the like to supply the raw material liquid from the raw material liquid storage unit 421 through the raw material liquid supply pipe 425 to the storage cavity 415 of the head body 411. In one example, the raw material liquid supply drive unit 422 is a pump. In another example, the raw material liquid supply drive unit 422 pressure-feeds the raw material liquid from the raw material liquid storage unit 421 to the storage cavity 415 by supplying gas to the raw material liquid storage unit 421. The storage cavity 415 is capable of storing the raw material liquid supplied through the raw material liquid supply pipe 425.

[0045] The raw material liquid supply adjustment unit 423 adjusts the flow rate, pressure, etc. of the raw material liquid supplied to the electrospinning head 41. In one example, the raw material liquid supply adjustment unit 423 includes a control valve capable of controlling the flow rate, pressure, etc. of the raw material liquid. In this case, the raw material liquid supply adjustment unit 423 adjusts the raw material liquid to an appropriate flow rate, pressure, etc. based on the viscosity of the raw material liquid and the structure of the electrospinning nozzle 412. In another example, the raw material liquid supply adjustment unit 423 can switch between supplying and stopping the supply of the raw material liquid from the raw material liquid storage unit 421 to the electrospinning head 41. In this case, the raw material liquid supply adjustment unit 423 is, for example, a switching valve.

[0046] It is not always necessary to provide the raw material liquid supply driver 422 and the raw material liquid supply adjuster 423. In one example, the raw material liquid storage unit 421 is provided vertically above the head body 411, and the raw material liquid is supplied from the raw material liquid storage unit 421 to the electrospinning head 41 by utilizing gravity. In this case, by adjusting the difference in height between the head body 411 and the raw material liquid storage unit 421, it is possible to switch between supplying and stopping the supply of the raw material liquid.

[0047] In the embodiment, the electrospinning head 41 provided in the electrospinning machine 40b as an electrospinning unit for ejecting the raw material of the insulating fiber film from its ejection port is not limited to the one having the structure shown in the figure. In addition to the electrospinning head 41 provided with one or more electrospinning nozzles 412 as provided in the electrospinning machine 40b shown in Fig. 4, the electrospinning machine may be provided with an electrospinning nozzle to which the raw material is directly supplied from the raw material liquid supply source 42 as in the electrospinning machine 40a shown in Fig. 1 as an electrospinning unit, or a nozzleless electrospinning head that does not have an electrospinning nozzle but has a flow path and an ejection port for the raw material liquid at a position other than the nozzle, although a specific example is not shown.

[0048] The power source 43 can apply a voltage to the electrospinning head 41. When a voltage is applied to the electrospinning head 41, a voltage of a predetermined polarity is applied to each of the electrospinning nozzles 412 via the head body 411. When a plurality of electrospinning nozzles 412 are provided, voltages of the same polarity are applied to the electrospinning nozzles 412. When a voltage is applied to the electrospinning head 41 by the power source 43 as described above, and the raw material liquid is supplied to the electrospinning head 41 by the raw material liquid supply adjustment unit 423, the raw material liquid is charged to the same polarity as the electrospinning nozzle 412 (electrospinning head 41).

[0049] In one example, terminals (not shown) electrically connected to each of the electrospinning nozzles 412 may be provided, and the power source 43 may apply a voltage to each of the electrospinning nozzles 412 via the terminals. In this case, it is not necessary to form the head body 411 from a conductive material. In addition, the polarity of the voltage applied to each of the electrospinning nozzles 412 may be positive or negative. In the example of each figure, the power source 43 is a DC power source and applies a positive voltage to each of the electrospinning nozzles 412.

[0050] In the example of FIG. 4, the substrate 8 is grounded. Therefore, when a positive voltage is applied to each of the electrospinning nozzles 412, the voltage of the substrate 8 to ground is 0 V or approximately 0 V. In another example, the substrate 8 is not grounded. For example, as in the electrospinning machine 40a shown in FIG. 1, a voltage of the opposite polarity to that of each of the electrospinning nozzles 412 is applied to the guide roller 90 provided at the second position 4a by the power source 43 or a power source other than the power source 43. By applying a voltage to the guide roller 90 made of a conductive material, a voltage can be indirectly applied to the substrate 8.

[0051] The electrospinning nozzle 412 is disposed so that the nozzle 418 faces the side surface of the long side of the substrate 8. Here, the side surface facing the nozzle 418 refers to the edge portion along the long side of the strip-shaped substrate 8. That is, the side surface of the substrate 8 here is a surface intersecting with the main surface of the substrate 8. In other words, the side surface of the substrate 8 is a surface along the thickness direction of the substrate 8. That is, the electrospinning unit (electrospinning nozzle 412) is installed so that the flow direction 419 of the flow path 417 is parallel to the main surface of the substrate 8. The aperture of the nozzle 418 is, for example, 200 μm or more and 500 μm or less.

[0052] In a state where the raw material liquid is supplied to the electrospinning head 41 by the raw material liquid supply source 42, a voltage is applied to the electrospinning head 41 by the power source 43, so that the raw material liquid is charged to the same polarity as the electrospinning head 41. Alternatively, a voltage is applied to the electrospinning head 41, and the raw material liquid is supplied to the electrospinning head 41, so that the raw material liquid is charged to the same polarity as the electrospinning head 41. When the raw material liquid is charged to the same polarity as the electrospinning head 41, a potential difference is generated between the raw material liquid in the electrospinning head 41 (electrospinning nozzle 412) and the substrate 8. The raw material liquid is ejected toward the substrate 8 due to the potential difference between the electrospinning head 41 (electrospinning nozzle 412) and the substrate 8. When the raw material liquid is ejected toward the substrate 8 from each ejection port 418 of the electrospinning nozzle 412, the fibers 82 are deposited on the surface of the substrate 8, and the deposited fibers 82 form an insulating fiber membrane 83. That is, the insulating fibrous membrane 83 is formed by electrospinning (also called electric field spinning or electric charge induced spinning).

[0053] The voltage applied between the electrospinning head 41 and the substrate 8, i.e., the potential difference between each of the electrospinning nozzles 412 and the substrate 8, is adjusted to an appropriate value according to the type of polymer contained in the raw material liquid and the distance of each of the electrospinning nozzles 412 to the substrate 8. In one example, a DC voltage of 10 kV or more and 100 kV or less is applied between each of the electrospinning nozzles 412 and the substrate 8.

[0054] The raw material liquid ejected from the ejection port 418 of the electrospinning nozzle 412 moves along the in-plane direction of the main surface of the substrate 8 while changing into the fibers 82, and is deposited on the substrate 8. That is, the raw material liquid is ejected in a direction parallel to the main surface of the substrate, and is deposited on the substrate 8 as the fibers 82. The trajectory of the raw material liquid / fibers 82 that is ejected from each ejection port 418 of the electrospinning nozzle 412 until it is deposited on the substrate 8 as the fibers 82 may be roughly parallel or approximately parallel to the main surface of the substrate 8, for example. By ejecting the raw material liquid from the ejection port 418 of the electrospinning nozzle 412 that is installed so that the flow direction 419 of the flow path 417 is parallel to the side of the substrate 8, the ejection direction of the raw material liquid and the trajectory of the raw material liquid / fibers 82 can be parallel or approximately parallel to the main surface of the substrate 8. In addition, since the trajectory of the raw material liquid is guided in the direction from the nozzle 418 to the substrate 8 by the potential difference between the charged raw material liquid and the substrate 8, the effect of gravity on the raw material liquid / fiber 82 does not need to be taken into consideration.

[0055] Since the primer solution 300 is applied to the main surface of the substrate 8 at the first position 3a to form the primer coating 81, the fibers 82 are deposited on both the front and back main surfaces of the substrate 8 in a state suitable for the insulating fiber film 83, even if the raw material liquid is sprayed in a direction along the main surface of the substrate 8. Some of the fibers 82 extend beyond the area of ​​the main surface of the substrate 8 and extend beyond the side surface (the opposite edge across the short side direction of the substrate 8) opposite the side surface of the substrate 8 facing the spray nozzle 418. Since the main surface of the substrate 8 is covered with the primer coating 81, the protruding width of the fibers 82 can be reduced compared to the case where the primer coating 81 is not provided. By reducing the protruding of the fibers 82, it is not necessary to remove the excess fibers 82, and the manufacturing efficiency is improved. Furthermore, since the primer coating 81 is provided on the main surface of the substrate 8, the fibers 82 can be deposited on the main surface in a larger amount, and the material efficiency in the manufacturing process is improved.

[0056] The fibers 82 are also deposited on the side surface of the substrate 8 facing the nozzle 418 of the electrospinning nozzle 412, which corresponds to the edge surface of the long side of the substrate 8 having a belt shape. On the other hand, although the fibers 82 protrude from the long side opposite the side surface facing the nozzle 418 as described above, the fibers 82 are not easily deposited on this opposite side surface itself. In other words, the side surface of the substrate 8 opposite the side surface facing the nozzle 418 is located in a blind spot for the nozzle 418.

[0057] In order to deposit the fibers 82 on the side surfaces along the long sides of the strip-shaped substrate 8, it is desirable to eject the raw material liquid toward the side surfaces of the long sides of the substrate 8 from both directions along the short side direction of the substrate 8. That is, as in the example shown in the figure, it is desirable to install one or more electrospinning nozzles 412 so that the ejection port 418 faces the side surface of one long side of the substrate 8, and install one or more other electrospinning nozzles 412 so that the ejection port 418 faces the side surface of the other long side of the substrate 8. However, in order to avoid the influence of interference between the electrospinning nozzles 412 to which voltages of the same polarity are applied, it is important to note that the ejection ports 418 do not face each other (through the substrate 8). For example, the electrospinning nozzles 412 provided on one long side of the substrate 8 and the electrospinning nozzles 412 provided on the other long side are respectively installed in a shifted arrangement along the transport path 100 of the substrate 8.

[0058] The control unit (controller) 44 is, for example, a computer. The control unit 44 includes a processor or integrated circuit (control circuit) including a CPU (Central Processing Unit), an ASIC (Application Specific Integrated Circuit) or an FPGA (Field Programmable Gate Array), and a storage medium such as a memory. The control unit 44 may include only one integrated circuit or multiple integrated circuits. The control unit 44 performs processing by executing a program or the like stored in a storage medium or the like. The control unit 44 controls the drive of the raw material liquid supply drive unit 422, the operation of the raw material liquid supply adjustment unit 423, the output from the power source 43, and the like.

[0059] As shown in FIG. 1, while the substrate 8 is conveyed along the conveying path 100, the raw material liquid / fiber 82 is ejected toward the side surface of the substrate 8, so that the insulating fiber membrane 83 can be continuously formed along the longitudinal direction of the substrate 8. As described above, the production does not have to be continuous. For example, the insulating fiber membrane 83 may be sequentially formed on the substrate 8 having a predetermined length in the longitudinal direction. In this case, in order to form the insulating fiber membrane 83 over the entire length of the substrate 8, the substrate 8 may be made movable, or the electrospinning unit may be moved along the longitudinal direction of the substrate 8. In such a case, the raw material liquid may be ejected alternately from an electrospinning unit whose ejection port faces a side surface along one of the longitudinal sides of the substrate 8 and from an electrospinning unit whose ejection port faces a side surface along the other longitudinal side.

[0060] As an embodiment different from the continuous roll-to-roll method shown in FIG. 1, a method for forming an insulating fiber membrane 83 on a substrate 8 by electrospinning using a sheet-type method will be described with reference to FIG.

[0061] FIG. 5 is a perspective view showing a schematic view of an embodiment of forming an insulating fiber film by a sheet-feed method. The electrospinning machine 40c for forming an insulating fiber film by a sheet-feed method includes a belt 48 for conveying the substrate 8 held by a jig 46, and an electrospinning nozzle 412 for ejecting the raw material liquid toward the substrate 8. At the second position 4c, the conveying path of the belt 48 is defined by a guide roller 90. The belt 48 is conveyed by driving a motor (not shown). A jig 46 having a stand 45 is placed on the belt 48, and the substrate 8 is held by the jig 46. The electrospinning nozzle 412 is arranged so that the ejection port faces the side surfaces along the long sides on both sides of the substrate 8 held by the jig 46. The raw material liquid is supplied to the electrospinning nozzle 412, but the supply source of the raw material liquid is omitted for the sake of simplicity of the drawing. A power supply 43 is installed so as to be capable of applying a voltage of one polarity to the electrospinning nozzle 412 and a voltage of the opposite polarity to the guide roller 90 .

[0062] The substrate 8 is cut to a predetermined length in the longitudinal direction of the band shape, and may have, for example, a rectangular shape. The dimensions of the rectangular shape are adjusted according to the size of the desired composite electrode, and for example, the length of the long side of the band shape may be 16 cm or more and 24 cm or less. The portion of the substrate 8 held by the jig 46 is masked by the jig 46, so that the fibers 82 are not deposited on this portion. Therefore, the portion of the substrate 8 held by the jig 46 is cut off in the manufacture of the composite electrode, so that it is desirable to make the dimension of the substrate 8 in the long side direction longer than the long side length of the electrode foil of the desired composite electrode.

[0063] In the illustrated example, the jig 46 has a structure that can be opened and closed about a hinge 47, thereby having a mechanism for holding the substrate 8. The structure of the jig 46 is not limited to the illustrated example, and may have, for example, a chuck that holds the substrate 8. It is desirable that the jig 46 has a structure that can hold the substrate 8 in a pulled state so that an appropriate tension is applied to the substrate 8 to prevent the substrate 8 from sagging.

[0064] The raw material liquid is charged by applying a voltage to the electrospinning nozzle 412 by the power source 43. In the example of Fig. 5, the power source 43 applies a voltage of the opposite polarity to each of the electrospinning nozzles 412 to the conductive guide roller 90. The belt 48, the base 45, and the jig 46 are also made of conductive materials, and a voltage of the opposite polarity to each of the electrospinning nozzles 412 is indirectly applied to the substrate 8. The guide roller 90 may be grounded.

[0065] As described above, due to the potential difference between the charged raw material liquid and the substrate 8, the raw material liquid is sprayed from the electrospinning nozzle 412 toward the side of the substrate 8, causing fibers 82 to deposit on the surface of the substrate 8 coated with the primer solution, thereby forming an insulating fibrous film.

[0066] As the belt 48 is transported, a jig 46 having a platform 45 and holding the substrate 8, which is placed on the belt 48, moves. In other words, the illustrated example corresponds to an embodiment in which the substrate 8 is movable. Instead of moving the substrate 8, the electrospinning nozzle 412 may be moved along the long side direction of the substrate 8.

[0067] By shifting the positional relationship between the substrate 8 and the electrospinning nozzle 412 along the longitudinal direction of the substrate 8, it is possible to form an insulating fiber membrane over the entire longitudinal length of the substrate 8. The raw material liquid may be ejected simultaneously from each of the electrospinning nozzles 412 arranged on both sides of the substrate 8, or the raw material liquid may be ejected alternately from each of the electrospinning nozzles 412. However, care must be taken so that the ejection ports of the electrospinning nozzles 412 do not face each other through the substrate 8. In addition, from the viewpoint of material efficiency, it is preferable to interrupt the ejection from the electrospinning nozzles 412 whose ejection ports are not facing the side surface of the substrate 8.

[0068] Alternatively, a plurality of electrospinning nozzles 412 may be arranged to correspond to the entire length of the substrate 8, and the raw material liquid may be sprayed to form an insulating fiber membrane without moving either the substrate 8 or the electrospinning nozzle 412. In this case, for example, the raw material liquid may be sprayed alternately from the electrospinning nozzle 412 arranged on one long side of the substrate 8 and the electrospinning nozzle 412 arranged on the other long side, thereby avoiding interference between the electrospinning nozzles 412 applied with the same polarity.

[0069] The application of the primer solution 300 at the first position 3a (or the first position 3b) may also be performed with the substrate 8 held by the jig 46. Moreover, drying at the downstream third position 5 may also be performed with the substrate 8 still held by the jig 46. The substrate 8, while being held by the jig 46, may be transported from the first position 3a to the second position 4c, from the second position 4c to the third position 5, and so on.

[0070] In this manner, for each rectangular unit cut to a predetermined length, the insulating fiber film can be formed by depositing the fibers 82 on the substrate 8 in a sheet-by-sheet manner.

[0071] As described above, the primer solution is applied to the substrate 8, and the raw material liquid is sprayed toward the side surface of the substrate 8 by electrospinning to deposit an insulating fiber film on the main surface of the substrate 8, thereby manufacturing the composite electrode 18. Fig. 1 shows a preferred embodiment in which drying and rolling are performed at a third position 5 and a fourth position 6 downstream of the second position 4a on the transport path 100 of the substrate 8.

[0072] In a preferred embodiment of the manufacturing apparatus 1 where drying is performed, a drying furnace 50 is installed at a third position 5 downstream of the second position 4a. The substrate 8 on which the insulating fiber film 83 is formed is transported from the electrospinning machine 40a to the drying furnace 50. The drying furnace 50 dries the primer coating 81 that coats the surface of the substrate 8 passing through the inside thereof and the insulating fiber film 83 formed on the surface of the substrate 8. The drying will be described in detail with reference to FIG. 6.

[0073] FIG. 6 is a cross-sectional view that shows the drying of the substrate 8 on which the primer coating 81 and the insulating fibrous film 83 are formed. The drying furnace 50 included in the third position 5 may include, for example, an infrared heater 51. The infrared heater 51 generates infrared rays. The infrared heater 51 radiates the generated infrared rays to the insulating fibrous film 83 formed on the surface of the substrate 8. The primer coating 81 and the insulating fibrous film 83 are heated by functional groups contained in the organic material, the solvent, etc. in the primer solution forming the primer coating 81 and the insulating fibrous film 83 absorbing the infrared rays radiated from the infrared heater 51, and the primer coating 81 and the insulating fibrous film 83 are heated, and the solvent contained in the primer solution forming the primer coating 81 and the insulating fibrous film 83 evaporates. As a result, the primer coating 81 is removed and the amount of the solvent contained in the insulating fibrous film 83 is reduced, and the substrate 8 and the insulating fibrous film 83 are dried.

[0074] Here, the infrared heater 51 preferably radiates infrared light having a wavelength of 10 μm or less corresponding to the maximum radiation intensity to the primer coating 81 and the insulating fiber film 83. In this case, the temperature of the infrared heater 51 becomes 17° C. (290 K) or more while radiating infrared rays. Here, many of the functional groups contained in the organic material and the solvent in the insulating fiber film 83 are likely to absorb infrared rays having a wavelength of 10 μm or less. Therefore, by radiating infrared rays in a spectrum having a wavelength of 10 μm or less corresponding to the maximum radiation intensity, the functional groups contained in the organic material and the solvent in the insulating fiber film 83 are more likely to absorb the radiated infrared rays, and the solvent contained in the insulating fiber film 83 is more likely to evaporate by heating. This allows the insulating fiber film 83 to be dried more appropriately. Among the functional groups contained in the solvent of the insulating fiber film 83, those that are likely to absorb infrared rays having a wavelength of 10 μm or less include a methyl group and a carbonyl group.

[0075] Moreover, it is more preferable that the wavelength corresponding to the maximum radiation intensity in the spectrum of the infrared ray radiated from the infrared heater 51 is 4 μm or more and 7 μm or less. By setting the wavelength corresponding to the maximum radiation intensity in the spectrum of the radiated infrared ray to 7 μm or less, the temperature of the infrared heater 51 becomes 137° C. (410 K) or more in the state of radiating infrared rays. Therefore, by radiating infrared rays with a spectrum in which the wavelength corresponding to the maximum radiation intensity is 7 μm or less, organic solvents having a boiling point of 100° C. or more are easily evaporated, and the primer solution forming the primer coating 81 and the solvent contained in the insulating fiber film 83 are more appropriately evaporated. Furthermore, by setting the wavelength corresponding to the maximum radiation intensity in the spectrum of the radiated infrared ray to 4 μm or more, the temperature of the infrared heater 51 becomes 451° C. (724 K) or less in the state of radiating infrared rays. This effectively prevents the temperature of the space in which the substrate 8 and the insulating fiber film 83 are dried from becoming excessively high in the state of radiating infrared rays.

[0076] The drying of the base material 8 and the insulating fiber film 83 in the drying furnace 50 is not limited to drying using infrared rays emitted from the infrared heater 51. In one example, in the drying furnace 50, the base material 8 and the insulating fiber film 83 may be dried using hot air instead of infrared rays emitted from the infrared heater 51.

[0077] The amount of solvent contained in the insulating fiber membrane 83 is reduced by drying in the drying furnace 50, so that the amount of solvent contained in the insulating fiber membrane 83 is kept low in the composite electrode manufactured by the manufacturing apparatus 1. This ensures the durability of the insulating fiber membrane 83 of the manufactured composite electrode, and also ensures the performance of products using the composite electrode.

[0078] For example, in a capacitor using a composite electrode manufactured by the manufacturing method and manufacturing apparatus according to the embodiment, the amount of solvent contained in the insulating fiber membrane 83 that functions as a separator is kept low, thereby improving the durability of the insulating fiber membrane 83 and the durability of the capacitor. Furthermore, by keeping the amount of solvent contained in the insulating fiber membrane 83 low, the internal resistance of the capacitor is kept low, making it possible to realize a high output of the capacitor. This ensures the performance of the capacitor.

[0079] A press machine 60 is installed at a fourth position 6 downstream of the third position 5. The press machine 60 includes a pair of press rollers 61. The press machine 60 is configured to press the insulating fiber membrane 83 formed on the surface of the substrate 8, and by rolling (pressing) the insulating fiber membrane 83 with the press machine, the insulating fiber membrane 83 is compressed, and the density and strength of the insulating fiber membrane 83 can be increased. Details of the pressing process will be described with reference to FIG. 7.

[0080] FIG. 7 is a schematic cross-sectional view showing an example of a press machine that may be provided in the manufacturing apparatus 1. The press machine 60 provided at the fourth position 6 on the transport path 100 of the substrate 8 includes a pair of press rollers 61. The pair of press rollers 61 is driven by, for example, an electric motor or the like. The substrate 8 having the insulating fiber membrane 83 formed on its surface is transported along the transport path 100 and sandwiched between the pair of press rollers 61. At this time, one press roller 61 presses the insulating fiber membrane 83 and the substrate 8 from one side in the thickness direction of the substrate 8, and the other press roller 61 presses the insulating fiber membrane 83 and the substrate 8 from the other side in the thickness direction of the substrate 8. In order to obtain an insulating fiber membrane 18c having a desired density and thickness as a separator of a composite electrode, appropriate adjustments can be made by pressing.

[0081] In the manufacturing apparatus 1, the press machine 60 preferably presses the insulating fiber film 83 formed on the surface of the substrate 8 at least before the substrate 8 is wound by the winder 70. In the manufacturing apparatus 1, the press machine 60 is preferably installed downstream of the drying furnace 50 in the transport path 100 of the substrate 8. By removing the primer solution 300 by drying before pressing by the press machine 60, it is possible to prevent the press roller 61 of the press machine 60 from becoming dirty. This makes it possible to reduce the frequency of washing the press roller 61 or to omit the washing process. In addition, by drying before pressing, it is possible to more reliably evaporate the solvent of the primer solution 300 and the raw material liquid.

[0082] In the manufacturing method of the composite electrode according to the embodiment described above, even though the electrospinning method is adopted, when a narrow substrate is used, the amount of fibers protruding outside the area of ​​the main surface of the substrate can be reduced. This will be described with reference to Figs. 8 and 9.

[0083] 8 and 9 each show a schematic diagram of the spread of fibers when the raw material liquid is ejected by the conventional electrospinning method. In each of FIGS. 8 and 9, a power source 43 applies a voltage between a substrate 88 and a substrate 8, and an electrospinning nozzle 412 having a nozzle base 412a and a needle portion 412b having a flow path (not shown) in which a flow direction 419 intersects (for example, perpendicular or substantially perpendicular) with the substrate 88 or the substrate 8, and the raw material liquid is supplied from a raw material liquid supply source 42 to the electrospinning nozzle 412 and charged, and the charged raw material liquid is ejected from the electrospinning nozzle 412 toward the main surfaces of the substrate 88 and the substrate 8, and the raw material liquid is deposited on the substrate 88 and the substrate 8 as fibers 82. When the fibers 82 are deposited on the main surfaces of the substrate 88 and the substrate 8 in a uniform distribution, the spread diameter 83a of the fibers 82 is typically about φ20 mm to 40 mm. On the other hand, if the substrate 88 has a rectangular main surface with each side dimension of 50 mm or more as in the example shown in FIG. 8, the fibers 82 can be deposited without protruding outside the substrate 88. On the other hand, if the short side width of the main surface of the substrate 8 is small and the spreading diameter 83a of the fibers 82 ejected toward the main surface of the substrate 8 exceeds the short side width of the main surface as in the example shown in FIG. 9, the fibers 82 will protrude outside the area of ​​the main surface of the substrate 8. As a specific example, if the spreading diameter 83a of the fibers 82 is φ20 mm or more for a substrate 8 with a short side width of 6 mm or less, the fibers 82 will protrude in total 14 mm or more in the short side direction of the substrate 8. Therefore, a process of removing the excess fibers 82 is added to the manufacturing process, and the material efficiency of the raw material liquid for the fibers 82 is low.

[0084] In the manufacturing method and manufacturing apparatus according to the embodiment, when fibers 82 formed from a raw material liquid are deposited on the surface of a substrate 8 by electrospinning, a primer treatment is performed in advance by applying a primer solution 300 to the surface of the substrate 8, and the raw material liquid is sprayed toward the side surface of the substrate 8 from a direction parallel or approximately parallel to the main surface of the substrate 8, not from a direction intersecting the main surface of the substrate 8, to deposit the fibers 82 on the main surface and side surface of the substrate 8. This method makes it possible to efficiently deposit the fibers 82 on the surface of the substrate 8, and to reduce the amount of the fibers 82 that protrude beyond the area of ​​the main surface of the substrate 8. An example of a composite electrode obtained by the manufacturing method and manufacturing apparatus according to the embodiment is shown in FIGS. 10 and 11.

[0085] FIG. 10 is a plan view that shows an example of a composite electrode and an example of its counter electrode obtained by the manufacturing method and manufacturing apparatus according to the embodiment described above. The composite electrode 18 includes an electrode foil 18a, an electrode terminal 18b, and an insulating fiber membrane 18c that is made of fiber 82 and functions as a separator. The composite electrode 18 has a configuration in which an electrode (electrode foil 18a) and a separator (insulating fiber membrane 18c) are integrated. The counter electrode 19 includes a counter electrode foil 19a and a counter electrode terminal 19b. The counter electrode 19 is a counter electrode for the composite electrode 18. The composite electrode 18 may be a composite anode in which an anode and a separator are integrated, and the counter electrode 19 may be a cathode. Alternatively, the composite electrode 18 may be a composite cathode in which a cathode and a separator are integrated, and the counter electrode 19 may be an anode. The illustrated example is the former combination, and in a typical standard, the cathode terminal (counter electrode terminal 19b) is shorter than the anode terminal (electrode terminal 18b) so that the anode terminal and the cathode terminal can be visually distinguished from each other.

[0086] The composite electrode 18 is suitably used as a composite electrode (composite anode or composite cathode) for an electrolytic capacitor. The counter electrode 19 can be an electrode (cathode or anode) for an electrolytic capacitor.

[0087] The electrode foil 18a and the counter electrode foil 19a have a belt shape. The electrode foil 18a and the counter electrode foil 19a are preferably conductive foils. The electrode foil 18a and the counter electrode foil 19a are more preferably conductive foils on whose surfaces an oxide coating functioning as a dielectric layer is chemically formed. In one example, each foil is an aluminum foil coated with an aluminum oxide coating. The electrode foil 18a is the substrate 8 described with reference to FIG. 1 and the like, and on its surface is supported an insulating fiber membrane 18c formed, for example, by depositing the fiber 82 at the second position 4a, drying at the third position 5, and rolling at the fourth position.

[0088] The electrode terminal 18b and the counter electrode terminal 19b may have, for example, a rod shape. The electrode terminal 18b and the counter electrode terminal 19b are electrically connected to the electrode foil 18a and the counter electrode foil 19a, respectively. Each terminal may be electrically connected, for example, by being crimped and fixed to the target foil. The long side of the rod shape of each terminal is oriented along, for example, the short side direction of the band shape of the target foil. Also, for example, one end of the rod shape of each terminal is aligned with one long side of the band shape of the target foil, and the other end protrudes from the other long side of the band shape of the foil. The electrode terminal 18b may be partially covered with an insulating fiber membrane 18c.

[0089] 11 is an enlarged view of a portion of the composite electrode 18 shown in FIG. 10 (an enlarged view of part A in FIG. 10). F The range of the insulating fiber membrane 18c in the short side direction of the composite electrode 18 is set to a short side width W F Outside, the protruding width W S The electrode foil 18a is protruding by a protruding width W S By manufacturing the composite electrode 18 by the manufacturing method and the manufacturing apparatus according to the embodiment, the protruding width W S The protrusion width W can be kept to 0.2 mm or less. SThe larger the protrusion width W on both sides, the more reliably the insulating fiber membrane 18c functions as a separator for electrically insulating the composite electrode 18 and the counter electrode 19. From the viewpoint of increasing the capacitance per volume of the capacitor, the protrusion width W on both sides is set to be 1.0 mm. S It is desirable to keep the protrusion width W to 0.2 mm or less. S It may further be 0.1 mm or less, and specifically, for example, may be 0.06 mm.

[0090] It is preferable to previously crimp and fix the electrode terminal 18b to the substrate 8 (electrode foil 18a) before forming the insulating fiber membrane 18c (insulating fiber membrane 83) on the surface of the electrode foil 18a. That is, it is preferable to crimp and fix the electrode terminal 18b to the substrate 8 prior to applying the primer solution 300 to the substrate 8. By crimping and fixing the electrode terminal 18b to the substrate 8 before forming the insulating fiber membrane 18c, it is possible to avoid partial removal of the insulating fiber membrane 18c that occurs when the electrode terminal 18b is electrically connected to the substrate 8 (electrode foil 18a) later. In addition, it is possible to avoid loss of function as a separator caused by the insulating fiber membrane 18c falling off when the electrode terminal 18b is crimped and fixed later. In addition, since the surface of the electrode terminal 18b can also be partially covered with the insulating fiber membrane 18c, it is possible to prevent short circuit via the electrode terminal 18b. In addition, as for the portions of the electrode terminal 18b where it is not desirable to cover with the insulating fiber membrane 18c, this can be dealt with, for example, by removing the excess insulating fiber membrane 18c later or by masking the portions not to be covered.

[0091] The counter electrode foil 19 a of the counter electrode 19 may have dimensions comparable to those of the electrode foil 18 a of the composite electrode 18 .

[0092] An electrolytic capacitor body, which is a main component of an electrolytic capacitor, can be produced using the composite electrode 18 and the counter electrode 19. Examples of an electrolytic capacitor body and an electrolytic capacitor are shown in Figures 12 and 13, respectively.

[0093] Fig. 12 is a partially exploded perspective view that diagrammatically illustrates an electrolytic capacitor body that uses the composite electrode 18 and the counter electrode 19. Fig. 13 is a perspective view that diagrammatically illustrates an electrolytic capacitor that uses this electrolytic capacitor body.

[0094] 12 includes the above-mentioned composite electrode 18 and counter electrode 19. The electrolytic capacitor body 16 is produced by overlapping the composite electrode 18 and counter electrode 19 so that the ends of the electrode terminal 18b and the counter electrode terminal 19b protruding from the electrode foil 18a and the counter electrode foil 19a, respectively, are aligned in the same direction, and by winding the laminate of the composite electrode 18 and the counter electrode 19 so that the electrode terminal 18b and the counter electrode terminal 19b extend from the wound end surface.

[0095] 13 includes an electrolytic capacitor body (not shown), a case 14, and a sealing material 15. The electrolytic capacitor 10 is constructed by housing the electrolytic capacitor body 16 in the case 14 and closing the opening of the case 14 with the sealing material 15 so as to expose the electrode terminal 18b and the counter electrode terminal 19b to the outside. The electrolytic capacitor 10 may further include an electrolyte (not shown) in the case 14. The electrolyte is impregnated into, for example, an insulating fiber membrane 18c.

[0096] The electrolytic capacitor 10 may be, for example, an aluminum electrolytic capacitor. In the case of the electrolytic capacitor 10 of this example, the electrode foil 18a is an aluminum foil coated with an aluminum oxide film. The electrolytic capacitor 10 includes a composite electrode 18 manufactured by the manufacturing method or device according to the embodiment as an anode or cathode. Therefore, the electrostatic capacitance per volume is large. The reason for this will be explained below.

[0097] Figures 14 and 15 show components of a conventional electrolytic capacitor. Figure 14 is a plan view that shows a schematic example of an electrode and a separator included in a conventional electrolytic capacitor. Figure 15 is a perspective view that shows a schematic example of an electrolytic capacitor body obtained by using the electrodes and separator shown in Figure 14.

[0098] The anode 11 includes a band-shaped anode foil 11a and an anode terminal 11b. The cathode 12 includes a band-shaped cathode foil 12a and a cathode terminal 12b. The cathode 12 is a counter electrode for the anode 11. The anode 11 and the cathode 12 may each have a similar configuration to the composite electrode 18 shown in FIG. 10 except that they do not have an insulating fiber membrane, or a similar configuration to the counter electrode 19 shown in FIG. 10.

[0099] The separator 13 is an electrically insulating member, such as insulating paper. The separator 13 may have a strip shape with dimensions similar to those of the anode 11 and the cathode 12, or slightly larger than those of the anode 11 and the cathode 12.

[0100] The electrolytic capacitor body 17 is produced by stacking the anode 11, one separator 13, the cathode 12, and another separator 13 in this order, and winding the resulting laminate so that the anode terminal 11b and the cathode terminal 12b extend from the winding end face.

[0101] Although Figures 14 and 15 show an example of an electrolytic capacitor body 17 using two separators 13 each having a long side length approximately equal to that of the anode 11 and cathode 12, various other forms of electrolytic capacitor bodies have been put into practical use.

[0102] In the electrolytic capacitor body 16 obtained by the manufacturing method and manufacturing apparatus according to the embodiment, unlike the conventional electrolytic capacitor body 17 using a separator 13 made of insulating paper or the like independent of the electrode, the insulating fiber film 18c is formed directly on the electrode foil 18a instead of overlapping the separator 13 on the electrode. The insulating fiber film 18c can be formed thin without impairing the function as a separator. Therefore, the electrolytic capacitor body 16 using the composite electrode 18 can realize a reduction in the volume of the electrolytic capacitor while maintaining the same capacitance as the conventional electrolytic capacitor body 17. Alternatively, the electrolytic capacitor body 16 using the composite electrode 18 can realize an improvement in the capacitance of the electrolytic capacitor while keeping the volume the same as the conventional electrolytic capacitor body 17. The improvement in capacitance per volume is also due to the fact that the insulating fiber film 18c in the composite electrode 18 manufactured by the manufacturing method and manufacturing apparatus according to the embodiment does not protrude beyond the area of ​​the main surface of the electrode foil 18a by a large amount.

[0103] In addition, when producing electrolytic capacitor body 16 using composite electrode 18, fewer materials are used compared to producing electrolytic capacitor body 17 which uses an independent separator 13 in addition to an electrode, so it is expected that the frequency of defective products will be reduced and the manufacturing yield will be improved.

[0104] According to one or more of the above-described embodiments, a method for manufacturing a composite electrode and an apparatus for manufacturing a composite electrode are provided. The composite electrode manufactured by the manufacturing method and the manufacturing apparatus includes a band-shaped substrate and an insulating fiber membrane provided thereon. The manufacturing method includes applying a primer solution to the substrate, and forming an insulating fiber membrane on the substrate by ejecting a charged raw material liquid in a direction parallel to a main surface intersecting with a side surface of the substrate and depositing the charged raw material liquid on the substrate. The manufacturing apparatus includes a conveying mechanism for conveying the substrate along a conveying path, an applicator for applying a primer solution to the substrate at a first position of the conveying path, and an electrospinning unit provided at a second position downstream of the first position of the conveying path, the flow direction of a flow path communicating with a nozzle for ejecting the raw material liquid being parallel to the main surface intersecting with the side surface of the substrate. According to the manufacturing method and the manufacturing apparatus, the composite electrode can be manufactured with high yield and material efficiency.

[0105] Although some embodiments of the present invention have been described, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their modifications are included in the scope and spirit of the invention, and are included in the scope of the invention and its equivalents described in the claims. The invention as originally claimed in the present application is set forth below. [1] Applying a primer solution to a strip-shaped substrate; The charged raw material liquid is ejected in a direction parallel to a main surface intersecting with a side surface of the substrate, and deposited on the substrate to form an insulating fibrous membrane on the main surface of the substrate; A method for manufacturing a composite electrode comprising the substrate and the insulating fiber membrane provided on the substrate, comprising: [2] The manufacturing method according to [1], wherein the width of the short side of the band-shaped substrate is 2 mm or more and 6 mm or less. [3] The method according to [1] or [2], wherein the primer solution contains one or more selected from the group consisting of ethylene glycol and γ-butyrolactone. [4] The manufacturing method according to any one of [1] to [3], wherein the application of the primer solution to the substrate is performed by a dipping method. [5] The manufacturing method according to any one of [1] to [3], wherein the application of the primer solution to the substrate is carried out by a spray method. [6] The manufacturing method described in any one of [1] to [5], wherein the band shape of the substrate has a rectangular shape, and the electrically charged raw material liquid is sprayed in a direction parallel to the main surface of the substrate and deposited on the substrate to form the insulating fiber membrane on the main surface of the substrate in a sheet-by-sheet manner for each rectangular shape unit. [7] The manufacturing method according to any one of [1] to [6], further comprising crimping and fixing an electrode terminal to the substrate prior to applying the primer solution to the substrate. [8] A conveying mechanism that conveys a strip-shaped substrate along a conveying path; a coater that coats the substrate with a primer solution at a first position of the transport path; an electrospinning unit provided at a second position of the transport path downstream of the first position of the transport path, the flow direction of a flow path communicating with an outlet for ejecting the raw material liquid being parallel to a main surface intersecting with a side surface of the substrate; An apparatus for manufacturing a composite electrode comprising: [9] The manufacturing apparatus described in [8], further comprising a drying furnace provided at a third position of the conveying path downstream of the second position of the conveying path, through which the substrate passes.

[10] The manufacturing apparatus described in [9], further comprising a press machine provided at a fourth position of the conveying path downstream of the third position of the conveying path, for rolling the insulating fiber membrane provided on the substrate.

[11] The manufacturing apparatus according to any one of [8] to

[10] , wherein the coater includes a sprayer that sprays the primer solution toward the substrate. [Explanation of symbols]

[0106] 1... manufacturing apparatus, 3a, 3b... first position, 4a, 4c... second position, 5... third position, 6... fourth position, 8... substrate, 10... electrolytic capacitor, 11... anode, 11a... anode foil, 11b... anode terminal, 12... cathode, 12a... cathode foil, 12b... cathode terminal, 13... separator, 14... case, 15... sealing material, 16, 17... electrolytic capacitor body, 18... composite electrode, 18a... electrode foil, 18b...electrode terminal, 18c...insulating fiber membrane, 19...counter electrode, 19a...counter electrode foil, 19b...counter electrode terminal, 20...unwinder, 21...reel, 30a, 30b...applicator, 31...container, 32...metering roll, 33...spray nozzle, 34...primer supply source, 40a, 40b, 40c...electrospinning machine, 41...electrospinning head, 42...raw material liquid supply source, 43...power source, 44...control unit , 45...base, 46...jig, 47...hinge, 48...belt, 50...drying furnace, 60...press machine, 61...press roller, 70...winder, 71...reel, 81...primer coating, 82...fiber, 83...insulating fiber membrane, 83a...spreading diameter, 88...substrate, 90...guide roller, 100...conveying path, 300...primer solution, 341...primer solution storage tank, 342...primer supply drive unit, 343...primer supply adjustment unit, 345...primer supply piping, 411...head body, 412...electrospinning nozzle, 412a...nozzle base, 412b...needle portion, 415...storage cavity, 417...flow path, 418...jet nozzle, 421...raw material liquid storage unit, 422...raw material liquid supply drive unit, 423...raw material liquid supply adjustment unit, 425...raw material liquid supply piping.

Claims

1. Applying a primer solution to a band-shaped substrate; forming an insulating fiber membrane on the main surface of the substrate by ejecting the charged raw material liquid toward a side surface of one of the long sides of the substrate in a direction parallel to a main surface intersecting the side surface of the substrate, and ejecting the charged raw material liquid toward a side surface of the other long side of the substrate at a position shifted along the longitudinal direction of the substrate, thereby depositing the charged raw material liquid on the substrate; A method for manufacturing a composite electrode comprising the substrate and the insulating fiber membrane provided on the substrate, comprising:

2. The method according to claim 1 , wherein the width of a short side of the band-shaped substrate is 2 mm or more and 6 mm or less.

3. The method according to claim 1 or 2, wherein the primer solution contains one or more selected from the group consisting of ethylene glycol and γ-butyrolactone.

4. The method according to claim 1 , wherein the primer solution is applied to the substrate by a dipping method.

5. The method according to claim 1 , wherein the primer solution is applied to the substrate by a spray method.

6. 6. The manufacturing method according to claim 1, wherein the band shape of the substrate has a rectangular shape, and the electrically charged raw material liquid is sprayed in a direction parallel to the main surface of the substrate and deposited on the substrate to form the insulating fiber membrane on the main surface of the substrate in a sheet-by-sheet manner for each rectangular shape unit.

7. The manufacturing method according to claim 1 , further comprising the step of crimping and fixing an electrode terminal to the substrate prior to applying the primer solution to the substrate.

8. A conveying mechanism that conveys a band-shaped base material along a conveying path; a coater that coats the base material transported along the transport path with a primer solution; an electrospinning unit including a jet outlet for jetting a raw material liquid onto the substrate transported along the transport path downstream of a position on the transport path where the primer solution is applied by the coater, the jet outlet being one or more jet outlets facing a side surface on one long side of the substrate and the jet outlet being the other or more jet outlets facing a side surface on the other long side of the substrate being shifted along a longitudinal direction of the substrate, and the flow direction of a flow path communicating with the jet outlet being parallel to a main surface intersecting with the side surface of the substrate; An apparatus for manufacturing a composite electrode comprising:

9. The manufacturing apparatus according to claim 8 , further comprising a drying furnace provided at a position downstream of the electrospinning unit on the transport path, through which the substrate passes.

10. The manufacturing apparatus according to claim 9 , further comprising a press machine, the press machine being provided at a position downstream of the drying oven in the transport path, for rolling the insulating fiber film provided on the substrate.

11. The manufacturing apparatus according to claim 8 , wherein the coater includes a sprayer that sprays the primer solution toward the substrate.

Images