WO2024143344A1 - 電解コンデンサおよびその製造方法 - Google Patents

電解コンデンサおよびその製造方法 Download PDF

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Publication number
WO2024143344A1
WO2024143344A1 PCT/JP2023/046608 JP2023046608W WO2024143344A1 WO 2024143344 A1 WO2024143344 A1 WO 2024143344A1 JP 2023046608 W JP2023046608 W JP 2023046608W WO 2024143344 A1 WO2024143344 A1 WO 2024143344A1
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WO
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Prior art keywords
separator
nonwoven fabric
fabric layer
electrolytic capacitor
laminate
Prior art date
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PCT/JP2023/046608
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English (en)
French (fr)
Japanese (ja)
Inventor
宗史 門川
泰洋 西村
満久 吉村
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2024567846A priority Critical patent/JPWO2024143344A1/ja
Publication of WO2024143344A1 publication Critical patent/WO2024143344A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/02—Diaphragms; Separators

Definitions

  • This disclosure relates to an electrolytic capacitor and a method for manufacturing the same.
  • a typical electrolytic capacitor includes an anode foil, a cathode foil, and a separator disposed between them. Capacitors using various separators have been proposed in the past.
  • Patent document 1 JP Patent Publication 2012-019006 A discloses claim 4 of "a capacitor element formed by winding or laminating multiple layers of anode aluminum foil and cathode aluminum foil, each having a dielectric layer made of aluminum oxide formed on the surface, with a separator between them, and an electrolytic capacitor in which the capacitor element is impregnated with a driving electrolyte and the capacitor element is housed in a cylindrical aluminum case with a bottom, and the opening of the aluminum case is sealed with a sealing material, the separator having a linear through hole, and the opening area on the front and back of the through hole is approximately the same.”
  • a driving electrolyte is used as the electrolyte.
  • electrolytic capacitors hybrid capacitors that use an electrolyte and a conductive polymer as the electrolyte are also known.
  • Hybrid capacitors are required to have a reduced equivalent series resistance (ESR).
  • ESR equivalent series resistance
  • the ESR of a hybrid capacitor is affected by the separator, electrolyte, and conductive polymer, and these influences must be taken into consideration.
  • one of the objectives of this disclosure is to provide a hybrid-type electrolytic capacitor with high performance.
  • the electrolytic capacitor includes a laminate and a liquid component impregnated in the laminate, the laminate including an anode foil having a dielectric layer formed on its surface, a cathode foil, a separator disposed between the anode foil and the cathode foil, and a conductive polymer disposed within the separator, the separator including a first nonwoven fabric layer exposed on the surface of the separator, and the first nonwoven fabric layer having through holes formed therein with a circle equivalent diameter in the range of 5 to 200 ⁇ m.
  • FIG. 1 is a photograph showing an example of a separator used in an electrolytic capacitor according to the present disclosure.
  • FIG. 2 is a cross-sectional view illustrating the electrolytic capacitor of the first embodiment.
  • FIG. 3 is a schematic view showing a portion of the laminate 10 included in the electrolytic capacitor 100 in a developed form.
  • FIG. 4A is a top view diagrammatically illustrating an example of a separator.
  • FIG. 4B is a schematic cross-sectional view taken along line IVB-IVB in FIG. 4A.
  • FIG. 5 is a cross-sectional view illustrating a schematic diagram of another example of the separator.
  • FIG. 6 is a cross-sectional view illustrating another example of the separator.
  • the electrolytic capacitor according to this embodiment may be referred to as an electrolytic capacitor (E) below.
  • the electrolytic capacitor (E) includes a laminate and a liquid component impregnated in the laminate.
  • the laminate may be referred to as a laminate (L) below.
  • the laminate (L) includes an anode foil having a dielectric layer formed on its surface, a cathode foil, a separator disposed between the anode foil and the cathode foil, and a conductive polymer disposed in the separator.
  • the separator includes a first nonwoven fabric layer exposed on the surface of the separator.
  • the first nonwoven fabric layer has through holes (a plurality of through holes) having a circle-equivalent diameter in the range of 5 to 200 ⁇ m formed therein.
  • the through holes having a circle-equivalent diameter in the range of 5 to 200 ⁇ m may be referred to as a "through hole (H)" below.
  • the separator plays an important role in isolating the anode and cathode while retaining the electrolyte (liquid component). Furthermore, in hybrid capacitors that use conductive polymers, the separator supports the conductive polymer and reduces the ESR. By making the separator thinner, the distance between the electrodes can be shortened, making it possible to reduce the ESR. However, making the separator thinner makes the anode and cathode more susceptible to short-circuiting. Increasing the density of the separator is an effective way to prevent short-circuiting. However, increasing the density of the separator can make it difficult to arrange the conductive polymer within the separator, which can lead to an increase in ESR. Furthermore, increasing the density of the separator can reduce the liquid circulation of the electrolyte.
  • the separator through-hole (H) does not necessarily have to have a conductive polymer disposed therein.
  • the separator through-hole (H) may have a conductive polymer disposed therein.
  • the through hole (H) may be formed after placing the conductive polymer in the separator. That is, the through hole (H) may be formed after placing the conductive polymer in the separator. In that case, the through hole (H) is formed without the conductive polymer placed therein. As a result, the circulation of the electrolyte is improved. Therefore, a hybrid electrolytic capacitor with excellent characteristics is obtained. In addition, by forming the through hole (H) after placing the conductive polymer, the shape of the through hole (H) is easily maintained.
  • the conductive polymer may be disposed in the separator after a through hole (H) is formed in the separator. That is, the conductive polymer may be disposed in the separator after a through hole (H) is formed in the separator. In this case, the conductive polymer is disposed inside the through hole (H). Therefore, a hybrid electrolytic capacitor with a low ESR is obtained. Generally, the concentration of the conductive polymer in the liquid used to dispose the conductive polymer is low. Therefore, the through hole (H) is not usually completely blocked by the conductive polymer.
  • FIG. 1 shows an example of an image of a separator (nonwoven fabric) with through holes (H). There are six through holes 13h (through holes (H)) in the image in Figure 1. As shown in Figure 1, there are almost no fibers inside the through holes 13h.
  • the ratio of the area of the through holes (H) to the surface area of the separator may be 0.05% or more, 0.1% or more, 1.0% or more, 5.0% or less, or 10% or less.
  • the ratio of the through holes (H) By increasing the ratio of the through holes (H), the effect of the through holes (H) is increased.
  • the ratio of the through holes (H) is too high, the function of the separator is reduced, so it is preferable to set the ratio of the through holes (H) to a certain value or less.
  • the through holes (H) are formed regularly.
  • the through holes (H) may be formed at equal intervals.
  • the shape of the through holes (H) (cross-sectional shape perpendicular to the direction in which the through holes (H) extend) is not particularly limited. The shape may be circular or approximately circular.
  • the average diameter Da of the through holes (H) is 5 ⁇ m or more, and may be 10 ⁇ m or more.
  • the average diameter Da is 200 ⁇ m or less, and may be 150 ⁇ m or less.
  • the average thickness T of the separator may be 10 ⁇ m or more, 20 ⁇ m or more, or 30 ⁇ m or more, and may be 100 ⁇ m or less, 70 ⁇ m or less, or 50 ⁇ m or less.
  • the average thickness T of the separator may be in the range of 10 to 100 ⁇ m (e.g., in the range of 20 to 70 ⁇ m).
  • the ratio Da/H of the average diameter Da of the through holes (H) to the average thickness T of the separator may be 0.025 or more, or 0.14 or more, and may be 20 or less, or 5 or less.
  • the ratio Da/H may be in the range of 0.025 to 20 (e.g., 0.14 to 5). By making the ratio Da/H 20 or less, short circuit resistance can be improved.
  • the average thickness of the first nonwoven fabric layer may be in the range of 0.05 to 0.4 times (e.g., in the range of 0.15 to 0.3 times) the average thickness of the second nonwoven fabric layer.
  • the present disclosure provides a separator for use in an electrolytic capacitor.
  • the separator is a separator for use in an electrolytic capacitor (E).
  • E electrolytic capacitor
  • the separator has been described above, so a duplicated description will be omitted.
  • a conductive polymer may or may not be disposed within the separator.
  • the following describes examples of the configuration and components of the electrolytic capacitor (E) according to this embodiment. Note that the configuration and components of the electrolytic capacitor (E) are not limited to the following examples. Components other than the separator may be those of known electrolytic capacitors (hybrid electrolytic capacitors).
  • the anode foil may be a metal foil.
  • the metal constituting the metal foil (anode foil) is preferably a valve metal or an alloy containing a valve metal. Examples of valve metals include aluminum, tantalum, niobium, and titanium.
  • the anode foil may be an aluminum foil.
  • the surface of the anode foil is preferably roughened. The surface of the anode foil may be roughened by a known method (e.g., etching).
  • the thickness of the anode foil may be in the range of 15 ⁇ m to 300 ⁇ m (e.g., 50 ⁇ m to 200 ⁇ m).
  • conductive polymers include polypyrrole, polythiophene, polyaniline, and derivatives thereof. These may be used alone or in combination.
  • the conductive polymer may be a copolymer of two or more monomers.
  • the derivative of a conductive polymer means a polymer having a conductive polymer as a basic skeleton.
  • an example of a derivative of polythiophene includes poly(3,4-ethylenedioxythiophene).
  • the conductive polymer may include a dopant.
  • the dopant may be selected depending on the conductive polymer, and known dopants may be used. Examples of dopants include naphthalenesulfonic acid, p-toluenesulfonic acid, polystyrenesulfonic acid, and salts thereof.
  • a conductive polymer is poly(3,4-ethylenedioxythiophene) (PEDOT) doped with polystyrenesulfonic acid (PSS).
  • the non-aqueous solvent may be an organic solvent or an ionic liquid.
  • non-aqueous solvents include ethylene glycol, propylene glycol, sulfolane, ⁇ -butyrolactone, and N-methylacetamide.
  • solutes e.g., organic salts
  • solutes include trimethylamine maleate, triethylamine borodisalicylate, ethyldimethylamine phthalate, mono 1,2,3,4-tetramethylimidazolinium phthalate, and mono 1,3-dimethyl-2-ethylimidazolinium phthalate.
  • a liquid (non-aqueous solvent) that does not contain a solute may be used as the liquid component.
  • the manufacturing method (M) includes a step (i) of laminating an anode foil having a dielectric layer formed on its surface, a cathode foil, and a separator such that the separator is disposed between the anode foil and the cathode foil to form a laminate (L), and a step (ii) of impregnating the laminate (L) with a liquid component.
  • the separator includes a first nonwoven fabric layer.
  • the manufacturing method (M) includes a step (a) and a step (b) prior to the step (i).
  • the step (a) is a step of forming through holes in the separator having a circle equivalent diameter in the range of 5 to 200 ⁇ m.
  • the step (b) is a step of disposing a conductive polymer in the separator.
  • the step (i) of forming the laminate is carried out according to the shape of the laminate.
  • the laminate (L) may be formed by stacking a flat anode foil, a flat cathode foil, and a flat separator in one direction.
  • a wound body (laminate (L)) may be formed by winding the anode foil, the cathode foil, and the separator so that the separator is disposed between the anode foil and the cathode foil.
  • the laminate (L) is impregnated with the liquid component.
  • the laminate (L) may be immersed in the liquid component.
  • the laminate (L) and the liquid component may be placed inside an exterior body, thereby impregnating the laminate (L) with the liquid component.
  • the laminate (L) and the liquid component are sealed in the exterior body. In this manner, the electrolytic capacitor (E) is manufactured.
  • the method for forming the through holes is not particularly limited.
  • the through holes may be formed by piercing the separator with needle-shaped protrusions.
  • a roller having many needle-shaped protrusions on its surface may be used. By rotating the roller and bringing it into contact with the separator, many through holes can be formed in the separator.
  • the liquid containing the conductive polymer is not particularly limited, and a liquid used to form a solid electrolyte layer of an electrolytic capacitor may be used.
  • the liquid containing the conductive polymer is obtained by dissolving or dispersing the conductive polymer in a liquid medium (solvent or dispersion medium).
  • the conductive polymer may be dispersed in the liquid in the form of particles.
  • liquid media include water, organic solvents, and mixtures thereof.
  • Organic solvents include lower alcohols and other organic solvents.
  • the concentration of the conductive polymer in the liquid may be in the range of 0.5% to 5% by mass.
  • the separator may include a second nonwoven fabric layer laminated to the first nonwoven fabric layer.
  • the bulk density of the second nonwoven fabric layer is less than the bulk density of the first nonwoven fabric layer.
  • FIG. 1 is a schematic diagram showing a state in which a part of a laminate 10 (wound body) included in the electrolytic capacitor 100 is developed.
  • Electrolytic capacitor 100 includes laminate (capacitor element) 10, liquid component (not shown), bottomed case 101, sealing member 102, seat plate 103, lead wires 104A and 104B, and lead tabs 105A and 105B.
  • Bottomed case 101 contains laminate 10 and the liquid component impregnated in laminate 10.
  • Sealing member 102 closes the opening of bottomed case 101.
  • Seat plate 103 covers sealing member 102.
  • Lead wires 104A and 104B pass through seat plate 103.
  • Lead tabs 105A and 105B connect lead wires 104A and 104B to the anode foil and cathode foil of laminate 10.
  • the vicinity of the open end of bottomed case 101 is drawn inward.
  • the open end of the bottomed case 101 is curled to crimp the sealing member 102.
  • the laminate 10 is formed by winding the anode foil 11, the cathode foil 12, and the separator 13 so that the separator 13 is disposed between the anode foil 11 and the cathode foil 12.
  • the outermost periphery of the wound body (laminate 10) is fixed with tape 15.
  • a dielectric layer (not shown) is formed on the surface of the anode foil 11.
  • a conductive polymer (not shown) is disposed within the separator 13.
  • the separator 13 is the separator described above.
  • the separator 13 has the above-mentioned through hole (H) (not shown) formed therein.
  • FIG. 4A A top view of an example of separator 13 is shown in FIG. 4A.
  • FIG. 4B A cross-sectional view taken along line IVB-IVB in FIG. 4A is shown in FIG. 4B. Note that the following diagrams are schematic diagrams, and in reality, the through holes 13h are smaller and there are more of them.
  • the example shown in Figures 4A and 4B is an example in which a conductive polymer is placed in the separator 13 and then through-holes 13h are formed.
  • the separator 13 shown in Figure 4A is composed of a first nonwoven fabric layer 13a and a second nonwoven fabric layer 13b laminated to the first nonwoven fabric layer 13a.
  • the bulk density of the second nonwoven fabric layer 13b is lower than the bulk density of the first nonwoven fabric layer 13a.
  • a plurality of through-holes 13h penetrating the separator 13 are formed in the separator 13.
  • the plurality of through-holes 13h are regularly arranged at regular intervals.
  • a conductive polymer (not shown) is placed in the portion other than the through-holes 13h (nonwoven fabric layer).
  • Figure 5 shows a cross-sectional view of a case where a conductive polymer is placed inside separator 13 after through-hole 13h is formed in separator 13.
  • conductive polymer 14 is placed inside through-hole 13h and inside separator 13 in parts other than through-hole 13h.
  • Figure 5 shows through-hole 13h as being completely filled with conductive polymer 14.
  • conductive polymer 14 does not completely fill through-hole 13h, and there are many voids inside (the same is true in Figure 6). Therefore, liquid components (such as an electrolyte) can move inside through-hole 13h in which conductive polymer 14 is placed.
  • An electrolytic capacitor, A laminate and a liquid component impregnated in the laminate comprises: an anode foil having a dielectric layer formed on a surface thereof; A cathode foil; a separator disposed between the anode foil and the cathode foil; A conductive polymer disposed in the separator, the separator includes a first nonwoven fabric layer exposed on a surface of the separator, The electrolytic capacitor, wherein the first nonwoven fabric layer has through holes formed therein, the through holes having a circle equivalent diameter in the range of 5 to 200 ⁇ m.
  • a method for manufacturing an electrolytic capacitor comprising the steps of: (i) forming a laminate by stacking an anode foil having a dielectric layer formed on a surface thereof, a cathode foil, and a separator such that the separator is disposed between the anode foil and the cathode foil; (ii) impregnating the laminate with a liquid component; the separator includes a first nonwoven layer; The method further comprises, before the step (i), A step (a) of forming through holes having a circle equivalent diameter in the range of 5 to 200 ⁇ m in the separator; and (b) disposing a conductive polymer within the separator.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
PCT/JP2023/046608 2022-12-27 2023-12-26 電解コンデンサおよびその製造方法 Pending WO2024143344A1 (ja)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5559714A (en) * 1978-10-27 1980-05-06 Nichicon Capacitor Ltd Electrolytic condenser
JPS56152228A (en) * 1980-04-25 1981-11-25 Nichicon Capacitor Ltd Electrolytic condenser
JPH06168848A (ja) * 1992-11-27 1994-06-14 Nippon Koudoshi Kogyo Kk 電解コンデンサ
JP2000331663A (ja) * 1999-05-18 2000-11-30 Nippon Kodoshi Corp セパレータ及び該セパレータを使用した電解コンデンサ，電気二重層コンデンサ，非水系電池
JP2006344506A (ja) * 2005-06-09 2006-12-21 Tomoegawa Paper Co Ltd 電子部品用セパレータ
JP2008016835A (ja) * 2006-06-08 2008-01-24 Kaneka Corp 電解コンデンサおよびその製造方法
JP2008047633A (ja) * 2006-08-11 2008-02-28 Saga Sanyo Industries Co Ltd 電解コンデンサおよびその製造方法
JP2018181733A (ja) * 2017-04-19 2018-11-15 ニッポン高度紙工業株式会社 電気化学素子用セパレータ及び電気化学素子

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5559714A (en) * 1978-10-27 1980-05-06 Nichicon Capacitor Ltd Electrolytic condenser
JPS56152228A (en) * 1980-04-25 1981-11-25 Nichicon Capacitor Ltd Electrolytic condenser
JPH06168848A (ja) * 1992-11-27 1994-06-14 Nippon Koudoshi Kogyo Kk 電解コンデンサ
JP2000331663A (ja) * 1999-05-18 2000-11-30 Nippon Kodoshi Corp セパレータ及び該セパレータを使用した電解コンデンサ，電気二重層コンデンサ，非水系電池
JP2006344506A (ja) * 2005-06-09 2006-12-21 Tomoegawa Paper Co Ltd 電子部品用セパレータ
JP2008016835A (ja) * 2006-06-08 2008-01-24 Kaneka Corp 電解コンデンサおよびその製造方法
JP2008047633A (ja) * 2006-08-11 2008-02-28 Saga Sanyo Industries Co Ltd 電解コンデンサおよびその製造方法
JP2018181733A (ja) * 2017-04-19 2018-11-15 ニッポン高度紙工業株式会社 電気化学素子用セパレータ及び電気化学素子

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