WO2024004721A1 - 固体電解コンデンサ - Google Patents

固体電解コンデンサ Download PDF

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Publication number
WO2024004721A1
WO2024004721A1 PCT/JP2023/022470 JP2023022470W WO2024004721A1 WO 2024004721 A1 WO2024004721 A1 WO 2024004721A1 JP 2023022470 W JP2023022470 W JP 2023022470W WO 2024004721 A1 WO2024004721 A1 WO 2024004721A1
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Prior art keywords
layer
conductive polymer
cathode
anode body
solid electrolytic
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PCT/JP2023/022470
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English (en)
French (fr)
Japanese (ja)
Inventor
孝拓 吉井
兄 廣田
義晴 片岡
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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 CN202380047932.9A priority Critical patent/CN119422217A/zh
Priority to JP2024530703A priority patent/JP7706082B2/ja
Publication of WO2024004721A1 publication Critical patent/WO2024004721A1/ja
Priority to US18/967,672 priority patent/US20250095924A1/en
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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
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • 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
    • H01G9/15—Solid electrolytic capacitors
    • 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
    • H01G9/008—Terminals
    • H01G9/012—Terminals specially adapted for solid capacitors
    • 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
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • 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
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes
    • 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
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes

Definitions

  • the present disclosure relates to solid electrolytic capacitors.
  • a solid electrolytic capacitor includes a capacitor element, a resin exterior body or case that seals the capacitor element, and an external electrode that is electrically connected to the capacitor element.
  • a capacitor element includes, for example, an anode body, a dielectric layer formed on the surface of the anode body, and a cathode portion covering at least a portion of the dielectric layer.
  • the cathode portion includes a conductive polymer (eg, a conjugated polymer and a dopant) covering at least a portion of the dielectric layer.
  • Conductive polymers are also called solid electrolytes.
  • the anode body is divided into a part covered with a cathode part (more specifically, a conductive polymer) (sometimes referred to as a cathode forming part) and a part not covered with a cathode part.
  • a cathode part more specifically, a conductive polymer
  • Ru a conductive polymer
  • Patent Document 1 discloses an anode, a dielectric layer provided on the surface of the anode, a first conductive polymer layer provided on the dielectric layer, and the first conductive polymer layer. a second conductive polymer layer provided above, a third conductive polymer layer provided above the second conductive polymer layer, and a third conductive polymer layer provided above the third conductive polymer layer; A solid electrolytic capacitor comprising a cathode layer provided, The first conductive polymer layer consists of a conductive polymer film formed by polymerizing pyrrole or a derivative thereof, and the second conductive polymer layer is formed by polymerizing thiophene or a derivative thereof. A solid electrolytic capacitor is proposed, characterized in that the third conductive polymer layer is made of a conductive polymer film formed by polymerizing pyrrole or a derivative thereof. ing.
  • Patent Document 2 includes an anode body having a porous part on the surface, a dielectric layer covering at least a part of the anode body, and a cathode part covering at least a part of the dielectric layer,
  • the cathode section includes a solid electrolyte layer covering at least a portion of the dielectric layer
  • the anode body includes a first anode body part in which the solid electrolyte layer is formed, and a second anode body part in which the solid electrolyte layer is not formed
  • the solid electrolyte layer includes a first solid electrolyte layer disposed within the porous portion and a second solid electrolyte layer disposed outside the porous portion,
  • the second anode body part proposes a solid electrolytic
  • Solid electrolytic capacitors are required to have excellent durability and provide high capacitance even when used for long periods of time or in high-temperature environments.
  • the capacitor element is an anode body having a porous portion at least in a surface layer, and having a first portion including a first end and a second portion including a second end opposite to the first end; a dielectric layer covering at least a portion of the anode body; a cathode portion covering at least a portion of the dielectric layer in the second portion; a separation part located between the first end and the second end of the anode body and insulating the first part and the cathode part; including;
  • the cathode portion includes at least a conductive polymer layer covering at least a portion of the dielectric layer,
  • the conductive polymer layer contains a conductive polymer, and has an inner layer filled in the voids of the porous portion and an outer layer protruding from the main surface of the anode body having the dielectric layer.
  • the separation part has an end A on the first end side and an end B on the second end side, When the length from the end B to the end of the cathode part on the second end side is L, in the region C included in the part within 0.05L from the end B of the porous part.
  • the filling rate is 46% or more, The filling rate relates to a solid electrolytic capacitor, which is the area ratio of the region C other than the voids.
  • FIG. 1 is a schematic cross-sectional view of a solid electrolytic capacitor according to an embodiment of the present disclosure.
  • the anode body can be divided into a part (second part) in which a cathode part (in particular, a conductive polymer layer) is formed, and a first part, in which a cathode part (in particular, a conductive polymer layer) is not formed.
  • the anode body includes a first end and a second end opposite the first end, the first portion includes the first end, and the second portion includes the second end.
  • an insulating separation section may be provided in order to ensure insulation between the first part and the cathode part.
  • a porous portion is provided at least on the surface layer of the anode body to increase the surface area.
  • the voids in the porous portion are filled with a conductive polymer via a dielectric layer.
  • the size of the void is small.
  • the filling rate of the conductive polymer tends to be low near the separation portion in the second portion of the anode body. This is thought to be because the processing liquid used to form the conductive polymer is repelled by the insulating separation part, making it difficult for the processing liquid to enter the void in the vicinity of the separation part.
  • a solid electrolytic capacitor In a solid electrolytic capacitor, if the filling rate of the conductive polymer in the void near the separation part is low (in other words, the porosity is high), it will pass through the remaining space of the porous part in this part to the first part side. Air may enter the second portion from the separation portion, or air may enter the second portion from near the boundary between the separating portion and the second portion. Furthermore, when the filling rate of the conductive polymer is low, the mechanical strength of the porous portion is also low. Therefore, in solid electrolytic capacitors, when stress is applied to the capacitor element due to deformation due to molding or voltage application, or when thermal stress is applied, the stress concentrates in the area near the separation part of the cathode part and the porous part is damaged.
  • the conductive polymer covering the second part may be oxidized and deteriorated, or dedoping (or decomposition of dopants, etc.) may occur, causing the conductivity of the conductive polymer to deteriorate.
  • sexuality decreases. Oxidative deterioration and dedoping of conductive polymers occur when solid electrolytic capacitors are used for long periods or at high temperatures (especially when voltage is applied for a long time or repeatedly). This is particularly noticeable, and the decrease in capacitance also becomes significant.
  • the capacitance can also be experimentally measured at the stage of the capacitor element before it is sealed with an exterior body.
  • the stress applied near the separation part of the cathode part is extremely small compared to the case of a solid electrolytic capacitor after sealing. Therefore, even if excellent results are obtained when evaluating capacitance using a capacitor element, when an evaluation is actually performed using a solid electrolytic capacitor, the decrease in capacitance is more noticeable than when using a capacitor element.
  • a solid electrolytic capacitor according to the present disclosure includes at least one capacitor element, the capacitor element has a porous portion at least in its surface layer, and a first portion including a first end portion and a first an anode body having a second portion including a second end portion opposite to the end portion; a dielectric layer covering at least a portion of the anode body; and a cathode portion covering at least a portion of the dielectric layer in the second portion. and a separation part located between the first end and the second end of the anode body and insulating the first part and the cathode part, the cathode part being at least one part of the dielectric layer.
  • the conductive polymer layer includes at least a conductive polymer layer covering the porous portion, and the conductive polymer layer includes a conductive polymer and an inner layer filled in the voids of the porous portion, and a main surface of the anode body having a dielectric layer.
  • the separating part has an end A on the first end side and an end B on the second end side, and the separating part has an end A on the first end side and an end B on the second end side.
  • the filling rate in the region C near the separation part By setting the filling rate in the region C near the separation part to 46% or more, the remaining space in the region C is reduced, and the mechanical strength is increased. Since the portion of the second portion near the separation portion with a high filling rate acts as a barrier, air intrusion from the first portion side to the second portion side of the anode body is reduced. In addition, diffusion of air in the second portion and from the second portion to the conductive polymer layer is suppressed. Therefore, even if solid electrolytic capacitors are used for long periods of time or at high temperatures (especially if voltage is applied for a long time or repeatedly), the conductive polymer will not deteriorate. By suppressing this and maintaining the high conductivity of the conductive polymer, a decrease in capacitance is suppressed.
  • solid electrolytic capacitors have high reliability when used for long periods of time or at high temperatures.
  • a decrease in capacitance of a solid electrolytic capacitor is suppressed even if a voltage is applied for a long time or repeatedly at high temperatures. , high durability against heat) can also be ensured.
  • a direction parallel to the direction from the first end to the second end of the anode body is referred to as the length direction of the anode body. More specifically, the length direction of the anode body is a direction connecting the center of the end surface of the first end and the center of the end surface of the second end.
  • the length direction of the cathode portion and the length direction of the capacitor element are each parallel to the length direction of the anode body.
  • the direction perpendicular to the length direction and thickness direction of the capacitor element is defined as the width direction of the capacitor element.
  • the length L from the end B of the separating section to the end on the second end side of the cathode section is a length in a direction parallel to the length direction of the cathode.
  • the filling rate is determined in the vicinity of the separation part in the cross section parallel to the length direction and the thickness direction (specifically, the part 0.05L long from the end B of the separation part) near the center in the width direction of the capacitor element. ) is obtained for a region C of a predetermined size.
  • the vicinity of the center in the width direction refers to an area within ⁇ 0.1 W from the center in the width direction of the capacitor element, where W is the maximum width of the portion where the cathode portion of the capacitor element is formed.
  • the angle when the angle is parallel to the thickness direction of the capacitor element, it also includes the case where the angle (acute angle) formed with the thickness direction is within the range of ⁇ 5°.
  • a sample for measuring the filling factor is prepared by cutting a solid electrolytic capacitor and exposing the above cross section by ion milling. An image of the exposed cross section is taken with an optical microscope, and this image is binarized to determine the area ratio that portions other than the voids occupy in the area C, and this area ratio is taken as the filling rate (%).
  • the binarization process is performed by the Otsu binarization method, and a threshold value that produces the greatest difference when dividing the color distribution in area C of the cross-sectional image into white and black is determined.
  • the color distribution of area C is divided into white and black using this threshold value, and the ratio (%) of white pixels to all pixels of area C is determined.
  • This ratio is determined for the region C of the porous portion on both main surface sides of the anode body in the above-mentioned cross section, and is averaged. The average value obtained is taken as the filling rate (%).
  • the ratio (%) of black pixels to all pixels in region C corresponds to the porosity.
  • the sum of the porosity and the filling rate is 100%.
  • the length L from the end B of the separating section to the end on the second end side of the cathode section is determined from the above-mentioned cross-sectional image.
  • the magnification of the cross-sectional image obtained by the optical microscope is 10 times to 30 times (for example, 20 times).
  • a digital microscope "VHX-6000" series manufactured by Keyence Corporation is used as the optical microscope.
  • region C is a rectangular region with a first side length of 15 ⁇ m or more and 20 ⁇ m or less, and a second side orthogonal to the first side length of 20 ⁇ m or more and 25 ⁇ m or less. It is preferable. In this case, the filling rate can be determined with high accuracy.
  • the first side of region C may or may not be parallel to the length direction or thickness direction of the capacitor element.
  • the second side of region C may or may not be parallel to the thickness direction or length direction of the capacitor element.
  • the anode body may have a core and a porous part formed integrally with both surfaces of the core, and the region C and the core
  • the shortest distance to the surface is preferably 0 ⁇ m or more and 5 ⁇ m or less. In this case, it is advantageous in reducing variations in the measured values of the filling factor.
  • the shortest distance between region C and the surface of the core is the shortest distance between region C and the average surface of the core (in other words, the average bottom surface of the porous portion) determined in the above cross-sectional image. It is.
  • the filling rate is determined by measuring each region C of the porous portion formed on both surface sides of the core portion and averaging them. It is preferable that both the shortest distance between each region C and the average bottom surface of the porous portion including each region C satisfy the above range.
  • the conductive polymer layer contains a monomer unit corresponding to at least one selected from the group consisting of a pyrrole compound, a thiophene compound, and an aniline compound. It may also contain a conjugated polymer containing.
  • the capacitor element includes an anode body, a dielectric layer that covers at least a portion of the anode body, a cathode portion that covers at least a portion of the dielectric layer in a second portion, and a separation portion that insulates the first portion and the cathode portion. including.
  • the anode body can include a valve metal, an alloy containing a valve metal, a compound containing a valve metal, and the like.
  • the anode body may contain one kind of these materials or a combination of two or more kinds.
  • the valve metal for example, aluminum, tantalum, niobium, and titanium are preferably used.
  • the anode body has a porous portion at least in the surface layer.
  • An anode body with a porous surface layer can be obtained by roughening the surface of a base material (such as a sheet-like (e.g., foil-like, plate-like) base material) containing a valve metal by, for example, etching. .
  • the surface roughening can be performed by, for example, etching treatment.
  • Such an anode body may have a core portion and a porous portion formed integrally with both surfaces of the core portion.
  • the thickness of the porous portion on one surface of the base material may be, for example, 30 ⁇ m or more. When the thickness of the porous portion on one surface of the base material is 40 ⁇ m or more, it tends to be difficult to highly fill the conductive polymer in the vicinity of the separation portion of the porous portion.
  • the conductive polymer can be highly filled in the vicinity of the separation portion, and a high filling rate can be ensured.
  • the thickness of the porous portion depends on the thickness of the base material, it may be 70 ⁇ m or less on one surface of the base material.
  • the anode body may be a porous molded body of particles containing a valve metal or a porous sintered body thereof. Note that in each of the porous molded body and the sintered body, the entire anode body usually has a porous structure. Each of the molded body and the sintered body may have a sheet-like shape, a rectangular parallelepiped, a cube, or a shape similar to these.
  • the anode body has a first part including a first end, and a second part including a second end opposite to the first end.
  • the first end and the second end are both longitudinal ends of the anode body.
  • a cathode section (particularly a conductive polymer layer) is formed in the second portion via a dielectric layer. Therefore, the second portion is sometimes referred to as a cathode forming portion.
  • the portion in which the separation portion is not formed is sometimes referred to as an anode portion (or an anode lead-out portion).
  • An anode lead terminal may be connected to the anode portion.
  • the dielectric layer is formed to cover at least a portion of the anode body.
  • the dielectric layer is an insulating layer that functions as a dielectric.
  • the dielectric layer is formed by anodizing the valve metal on the surface of the anode body by chemical conversion treatment or the like.
  • the surface of the dielectric layer has a fine uneven shape depending on the shape of the surface of the porous portion.
  • the dielectric layer may be formed of a material that functions as a dielectric layer.
  • the dielectric layer includes such a material, for example, an oxide of a valve metal.
  • the dielectric layer contains Ta 2 O 5 when tantalum is used as the valve metal, and the dielectric layer contains Al 2 O 3 when aluminum is used as the valve metal.
  • the dielectric layer is not limited to these specific examples.
  • the cathode portion is formed to cover at least a portion of the dielectric layer in the second portion.
  • the cathode section includes at least a conductive polymer layer (solid electrolyte layer) covering at least a portion of the dielectric layer.
  • the cathode portion may include a conductive polymer layer and a cathode extraction layer covering at least a portion of the conductive polymer layer. The conductive polymer layer and cathode extraction layer will be explained below.
  • the conductive polymer layer includes a conductive polymer layer.
  • the conductive polymer layer has an inner layer filled in the voids of the porous portion and an outer layer protruding from the main surface of the anode body having the dielectric layer.
  • a dielectric layer is formed on at least a portion of the inner wall of the gap.
  • the inner layer may be formed to adhere to the inner wall of the gap via a dielectric layer.
  • the main surface of the anode body having the dielectric layer is located at both ends in the thickness direction of the anode body (in other words, in the direction parallel to the stacking direction of each layer in the capacitor element) in the cross-sectional image for measuring the filling factor. It is an average surface located in each.
  • the conductive polymer layer has inner layers filled in the voids and side surfaces (on average located at both ends of the anode body in the width direction), even on the side surfaces and end surfaces other than the main surface.
  • the anode may have an outer layer protruding from the end surface (the average surface located at the end in the length direction of the anode body).
  • the filling rate in the region C included in the portion within 0.05L from the end B of the separation part of the porous part is 46% or more.
  • the filling rate is as high as 46% or more in the porous part near the separation part, which is originally difficult to be highly filled. This prevents air from entering the second part from the anode side, and even if the solid electrolytic capacitor is used for a long time with voltage applied or used at high temperatures, it will not be conductive.
  • High capacity can be maintained by suppressing polymer deterioration and maintaining high conductivity.
  • the filling rate may be 47% or more, or 47.4% or more. In these cases, the effect of maintaining high capacity is further enhanced and higher durability can be ensured.
  • the filling rate corresponds to the ratio of white pixels binarized by the Otsu binarization method as described above.
  • White pixels mainly correspond to the anode body, the conductive polymer layer (inner layer), and the dielectric layer. Therefore, when there are fewer voids, the filling rate tends to be higher.
  • the region C included in the porous portion of the second portion has a relatively high porosity before forming the conductive polymer layer. Therefore, in a solid electrolytic capacitor, when region C shows a high filling rate of 46% or more, it means that region C is highly filled with conductive polymer.
  • the upper limit of the filling rate is not particularly limited, it is difficult to set it to 100%, and it is usually 70% or less.
  • the conductive polymer that constitutes the conductive polymer layer includes, for example, a conjugated polymer and a dopant.
  • the conductive polymer may further contain additives, if necessary.
  • conjugated polymer examples include known conjugated polymers used in solid electrolytic capacitors, such as ⁇ -conjugated polymers.
  • conjugated polymer examples include polymers having a basic skeleton of polypyrrole, polythiophene, polyaniline, polyfuran, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, and polythiophene vinylene.
  • polymers having a basic skeleton of polypyrrole, polythiophene, or polyaniline are preferred.
  • the above-mentioned polymer only needs to contain at least one kind of monomer unit constituting a basic skeleton.
  • the monomer unit also includes a monomer unit having a substituent.
  • the above polymers also include homopolymers and copolymers of two or more types of monomers.
  • polythiophene includes poly(3,4-ethylenedioxythiophene) and the like.
  • conjugated polymers a conjugated polymer containing a monomer unit corresponding to at least one selected from the group consisting of a pyrrole compound, a thiophene compound, and an aniline compound is preferred.
  • the pyrrole compound include compounds that have a pyrrole ring and can form a repeating structure of corresponding monomer units.
  • the thiophene compound include compounds that have a thiophene ring and can form a repeating structure of corresponding monomer units. These compounds can be linked at the 2- and 5-positions of the pyrrole ring or thiophene ring to form a repeating structure of monomer units.
  • aniline compound examples include compounds that have a benzene ring and at least one (preferably one) amino group bonded to the benzene ring and can form a repeating structure of corresponding monomer units.
  • the aniline compound can form a repeating structure of monomer units by linking, for example, an amino group and a CH group (CH group constituting a benzene ring) at the p-position to the amino group.
  • the pyrrole compound may have a substituent at least one of the 3-position and 4-position of the pyrrole ring, for example.
  • the thiophene compound may have a substituent at least one of the 3-position and 4-position of the thiophene ring, for example.
  • the substituent at the 3-position and the substituent at the 4-position may be linked to form a ring condensed to a pyrrole ring or a thiophene ring.
  • Examples of the pyrrole compound include pyrrole which may have a substituent at least one of the 3-position and the 4-position.
  • Examples of the thiophene compound include thiophene which may have a substituent at least one of the 3-position and the 4 -position, alkylenedioxythiophene compounds (C2-4 alkylenedioxythiophene compounds such as ethylenedioxythiophene compounds, etc.) ).
  • Alkylene dioxythiophene compounds include those having a substituent on the alkylene group.
  • Examples of the aniline compound include aniline which may have a substituent at at least one of the o-position and the p-position relative to the amino group.
  • substituents include alkyl groups (such as C 1-4 alkyl groups such as methyl and ethyl groups), alkoxy groups (such as C 1-4 alkoxy groups such as methoxy and ethoxy groups), hydroxy groups, hydroxyalkyl groups ( hydroxyC 1-4 alkyl groups such as hydroxymethyl group, etc.) are preferred, but are not limited thereto.
  • alkyl groups such as C 1-4 alkyl groups such as methyl and ethyl groups
  • alkoxy groups such as C 1-4 alkoxy groups such as methoxy and ethoxy groups
  • hydroxy groups such as C 1-4 alkyl groups such as methoxy and ethoxy groups
  • hydroxyalkyl groups hydroxyC 1-4 alkyl groups such as hydroxymethyl group, etc.
  • each substituent may be the same or different.
  • a conjugated polymer containing at least a monomer unit corresponding to pyrrole, or a conjugated polymer containing at least a monomer unit corresponding to a 3,4-ethylenedioxythiophene compound (such as 3,4-ethylenedioxythiophene (EDOT)) (PEDOT, etc.) may also be used.
  • the conjugated polymer containing at least a monomer unit corresponding to pyrrole may contain only a monomer unit corresponding to pyrrole, and in addition to the monomer unit, a monomer corresponding to a pyrrole compound other than pyrrole (such as a pyrrole having a substituent) May include units.
  • a conjugated polymer containing at least a monomer unit corresponding to EDOT may contain only a monomer unit corresponding to EDOT, or in addition to the monomer unit, it may also contain a monomer unit corresponding to a thiophene compound other than EDOT.
  • the conductive polymer layer may contain one type of conjugated polymer or a combination of two or more types.
  • the weight average molecular weight (Mw) of the conjugated polymer is not particularly limited, but is, for example, 1,000 or more and 1,000,000 or less.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) in terms of polystyrene. Note that GPC is usually measured using a polystyrene gel column and water/methanol (volume ratio 8/2) as a mobile phase.
  • Examples of the dopant include at least one selected from the group consisting of anions and polyanions.
  • anion examples include sulfate ion, nitrate ion, phosphate ion, borate ion, organic sulfonate ion, carboxylate ion, etc., but are not particularly limited.
  • dopants that generate sulfonic acid ions include benzenesulfonic acid, p-toluenesulfonic acid, and naphthalenesulfonic acid.
  • polyanions include polymer anions.
  • the conductive polymer layer may include, for example, a conjugated polymer containing a monomer unit corresponding to a thiophene compound and a polymer anion.
  • polymer anions include polymers having multiple anionic groups. Such polymers include polymers containing monomer units having anionic groups. Examples of the anionic group include a sulfo group and a carboxy group. It is preferable that the polymer anion has at least a sulfo group.
  • the anionic group of the dopant may be contained in a free form, an anionic form, or a salt form, or may be contained in a form bound or interacted with a conjugated polymer. Good too. In this specification, all of these forms may be simply referred to as an "anionic group,” “sulfo group,” or “carboxy group.”
  • polymer anion having a sulfo group examples include polymer type polysulfonic acid.
  • polymer anions include polyvinylsulfonic acid, polystyrenesulfonic acid (including copolymers and substituted products with substituents), polyallylsulfonic acid, polyacrylsulfonic acid, polymethacrylsulfonic acid, poly(2- Examples include acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid, polyestersulfonic acid (aromatic polyestersulfonic acid, etc.), and phenolsulfonic acid novolak resin.
  • the polymer anion is not limited to these specific examples.
  • the amount of dopant contained in the conductive polymer layer is, for example, 10 parts by mass or more and 1000 parts by mass or less, 20 parts by mass or more and 500 parts by mass or less, or 50 parts by mass, based on 100 parts by mass of the conjugated polymer. It may be more than 200 parts by mass or less.
  • the inner layer and the outer layer may be a single layer, or may have different compositions.
  • Each of the conductive polymer layer, inner layer, and outer layer may be a single layer or may be composed of multiple layers.
  • the conductive polymers contained in each layer may be the same or different.
  • the dopants contained in each layer may be the same or different.
  • a layer for increasing adhesion may be interposed between the dielectric layer and the conductive polymer layer.
  • additives include known additives (for example, coupling agents, silane compounds) added to the conductive polymer layer, known conductive materials other than conductive polymers, and water-soluble polymers.
  • the conductive polymer layer (or each layer constituting the conductive polymer layer) may contain one type of these additives or a combination of two or more of these additives.
  • the additives contained in each layer may be the same or different.
  • Examples of the conductive material as an additive include at least one selected from the group consisting of conductive inorganic materials such as manganese dioxide, and TCNQ complex salts.
  • the conductive polymer layer generally uses a liquid composition (solution or liquid dispersion, etc.) containing a conductive polymer, or a liquid composition (polymerization liquid) containing a conjugated polymer precursor and a dopant. It is formed by in-situ polymerization (chemical polymerization, electrolytic polymerization, etc.).
  • a portion of the inner layer is preferably formed by electrolytic polymerization.
  • the entire conductive polymer layer may be formed by electrolytic polymerization.
  • the parts other than the outer layer or the innermost layer of the conductive polymer layer may be formed by chemical polymerization, by using a liquid composition containing a conductive polymer, or by a combination of these. good.
  • Electrolytic polymerization can be performed using a three-electrode method.
  • at least a portion of the inner layer may be formed on the surface of the dielectric layer by electrolytically polymerizing a conjugated polymer precursor in the presence of a dopant in a three-electrode manner.
  • electrolytic polymerization is performed while the second portion of the anode body, on which a dielectric layer is formed, is immersed in a liquid composition (polymerization solution) containing a conjugated polymer precursor and a dopant.
  • electrolytic polymerization is performed using an anode body, a counter electrode, and a reference electrode.
  • the polymerization reaction can be controlled with high precision compared to the two-electrode system that uses an anode and a counter electrode, so a dense conductive polymer layer is easily formed, and the polymerization reaction can be easily formed near the separation part.
  • the filling rate of the porous portion can be increased.
  • the filling rate of the porous portion is increased not only in the vicinity of the separation portion but also in the entire second portion, and the intrusion of air can be reduced in the entire cathode portion compared to the conventional case. Therefore, in the entire conductive polymer layer, deterioration of the conductive polymer is suppressed, and the durability of the solid electrolytic capacitor can be improved.
  • Examples of the precursor of the conjugated polymer include raw material monomers for the conjugated polymer, oligomers and prepolymers in which multiple molecular chains of the raw material monomers are connected.
  • One type of precursor may be used, or two or more types may be used in combination. From the viewpoint of easily obtaining higher orientation of the conjugated polymer, it is preferable to use at least one type (especially monomer) selected from the group consisting of monomers and oligomers as the precursor.
  • the liquid composition used for electropolymerization usually contains a solvent.
  • the solvent include water, organic solvents, and mixed solvents of water and organic solvents (such as water-soluble organic solvents).
  • organic solvents such as water-soluble organic solvents.
  • the liquid composition may contain an oxidizing agent as necessary. Further, the oxidizing agent may be applied to the anode body before or after the liquid composition is brought into contact with the anode body on which the dielectric layer is formed.
  • oxidizing agents include compounds capable of producing Fe 3+ (ferric sulfate, etc.), persulfates (sodium persulfate, ammonium persulfate, etc.), and hydrogen peroxide.
  • One type of oxidizing agent may be used alone, or two or more types may be used in combination.
  • Three-electrode electrolytic polymerization is performed with an anode body on which a dielectric layer is formed, a counter electrode, and a reference electrode immersed in a liquid composition (polymerization solution).
  • a counter electrode for example, a Ti electrode is used, but the counter electrode is not limited thereto.
  • the reference electrode it is preferable to use a silver/silver chloride electrode (Ag/Ag + ).
  • the polymerization voltage is, for example, 0.6 V or more and 1.5 V or less. From the viewpoint of easily filling the voids of the porous portion with a conductive polymer, the polymerization voltage is preferably 0.6 V or more and less than 1 V, more preferably 0.7 V or more and 0.95 V or less, and 0.75 V or more and less than 1 V. It may be .9V or less.
  • electrolytic polymerization in a three-electrode manner at such a polymerization voltage, the polymerization reaction within the void can be precisely controlled. Therefore, the polymer chains of the conjugated polymer can be grown in the void in the presence of the dopant, and the void can be highly filled with conductive polymers.
  • the polymerization voltage is the potential of the anode body relative to the reference electrode (silver/silver chloride electrode (Ag/Ag + )).
  • the temperature at which electrolytic polymerization is performed is, for example, 5°C or higher and 60°C or lower, and may be 15°C or higher and 35°C or lower.
  • a precoat layer containing a conductive material on the surface of the dielectric layer prior to electrolytic polymerization.
  • the precoat layer may be formed using a liquid composition containing a conductive polymer.
  • the conductive polymer has a small particle size or that the conductive polymer is dissolved.
  • the concentration of the conductive polymer in the liquid composition is preferably relatively low.
  • the dry solid content concentration of the liquid composition used for electrolytic polymerization is, for example, 1.2% by mass or less.
  • the average primary particle diameter of the conductive polymer particles contained in the liquid dispersion is, for example, It is 100 nm or less, and may be 60 nm or less.
  • the average primary particle diameter of the conductive polymer particles is usually , 200 nm or more, and the dry solid content concentration is 2% by mass or more.
  • the liquid composition in the form of a solution includes, for example, a self-doped conductive polymer as the conductive polymer.
  • a self-doped conductive polymer has an acid group such as a sulfo group introduced into the polymer chain, and is easily dissolved in a solvent, so that a liquid composition in the form of a solution can be easily obtained. Therefore, the liquid composition easily permeates into the voids, and polymerization tends to occur more uniformly within the voids.
  • the precoat layer may be formed using a polyaniline compound (such as a soluble polyaniline compound) into which an acid group such as a sulfo group is introduced.
  • the conjugated polymer (or the polymer chain of the conductive polymer) of the precoat layer and the conjugated polymer formed by electrolytic polymerization may be of the same type or may be of different types.
  • the dopant of the precoat layer and the dopant used for electrolytic polymerization may be the same or different.
  • the weight average molecular weight (Mw) of the conductive polymer (or conjugated polymer) forming the precoat layer is preferably 1000 or more and 1 million or less, and 1000 or more and 850,000 or less. It may be.
  • the cathode extraction layer only needs to include at least a first layer that is in contact with the conductive polymer layer and covers at least a portion of the conductive polymer layer, and includes a first layer and a second layer that covers the first layer. You may be prepared.
  • the first layer include a layer containing conductive particles, a metal foil, and the like.
  • the conductive particles include at least one selected from conductive carbon and metal powder.
  • the cathode extraction layer may be composed of a layer containing conductive carbon (also referred to as a carbon layer) as the first layer and a layer containing metal powder or metal foil as the second layer. When using metal foil as the first layer, this metal foil may constitute the cathode extraction layer.
  • Examples of conductive carbon include graphite (artificial graphite, natural graphite, etc.).
  • the layer containing metal powder as the second layer can be formed, for example, by laminating a composition containing metal powder on the surface of the first layer.
  • a second layer is, for example, a metal particle-containing layer (for example, a metal paste layer such as a silver paste layer) formed using a composition containing metal powder such as silver particles and a resin (binder resin).
  • a thermoplastic resin can be used as the resin, it is preferable to use a thermosetting resin such as an imide resin or an epoxy resin.
  • the type of metal is not particularly limited. It is preferable to use a valve metal (aluminum, tantalum, niobium, etc.) or an alloy containing a valve metal as the metal foil. If necessary, the surface of the metal foil may be roughened. The surface of the metal foil may be provided with a chemical conversion coating, or may be provided with a metal (different metal) or non-metal coating that is different from the metal constituting the metal foil. Examples of the different metals and nonmetals include metals such as titanium and nonmetals such as carbon (conductive carbon, etc.).
  • the film of the above dissimilar metal or nonmetal may be used as the first layer, and the above metal foil may be used as the second layer.
  • a separator When using metal foil for the cathode extraction layer, a separator may be placed between the metal foil and the anode body (anode foil, etc.).
  • the separator is not particularly limited, and for example, a nonwoven fabric containing fibers of cellulose, polyethylene terephthalate, vinylon, polyamide (for example, aliphatic polyamide, aromatic polyamide such as aramid), etc. may be used.
  • the separation part is located between the first end and the second end.
  • the separation part is provided to insulate the first part (more specifically, the anode part) and the cathode part.
  • the separation portion is provided with a predetermined width, for example, in a portion where the porous portion is formed between the first end portion and the second end portion of the anode body.
  • the separation part may be formed, for example, at the end of the first part on the second part side.
  • a cathode section may be formed at the end of the surface of the separation section on the second end side.
  • the insulating region may be provided from the end of the first part on the second part side to the end of the second part on the first part side. From the viewpoint of more reliably ensuring insulation between the first part and the cathode part, it is preferable that the separation part is not provided in the second part.
  • the porous portion may be compressed in the thickness direction of the anode body. Further, in the region of the anode body where the separation portion is formed, the porous portion may be removed as necessary. In these cases, it is possible to further suppress air from entering from the anode section side to the second section side through the gap near the separation section.
  • the separation part includes an insulating material, for example, an insulating resin material or a cured product thereof.
  • the resin material include thermoplastic resins (or compositions thereof), curable resin materials (curable resin compositions, etc.), and the like.
  • the separation section may include an insulating material filled in the voids of the porous section, an insulating material disposed on the surface of the porous section, or both.
  • the separation part may include a cured insulating material formed in the void of the porous part and a cured insulating material formed on the main surface of the anode body with a dielectric layer interposed therebetween. .
  • the separation section may include a sheet-like insulating material such as an insulating tape attached to the main surface of the anode body.
  • the separation section may include a cured insulating material formed in the voids of the porous section and a sheet-like insulating material such as an insulating tape attached to the main surface of the anode body.
  • resin materials include curable resins (polyimide resin, silicone resin, phenol resin, urea resin, melamine resin, unsaturated polyester, furan resin, polyurethane, silicone resin, curable acrylic resin, epoxy resin, etc.), Photoresists, thermoplastic resins (eg, polyamide, polyamideimide, thermoplastic polyimide, polyphenylene sulfone resin, polyether sulfone resin, cyanate ester resin, fluororesin), and the like can be mentioned.
  • the resin material may contain one type of these resins or a combination of two or more types.
  • the resin material includes resin precursors (monomers, oligomers, prepolymers, etc.) as well as resins that are polymers, depending on the type of resin.
  • the curable resin material may be a one-component curable type or a two-component curable type.
  • the resin composition may also contain at least one selected from the group consisting of a curing agent, a curing accelerator, a polymerization initiator, a catalyst, a coupling agent, and the like.
  • the resin composition may also contain known additives used for forming separation parts of capacitor elements, if necessary. Examples of such additives include flame retardants, fillers, colorants, mold release agents, and inorganic ion scavengers.
  • the separation part can be formed, for example, by a process including a substep of filling the pores of the porous part with a treatment liquid containing a resin composition and a solvent and curing the resin composition.
  • a first step of preparing an anode body having a porous part on at least the surface layer, and forming a dielectric layer on the surface of the porous part is performed prior to the step of forming the separation part (third step).
  • a second step is performed.
  • the explanation regarding the anode body and the dielectric layer can be referred to.
  • a cathode part including a conductive polymer layer and the like is formed on the second part of the anode body via a dielectric layer (fourth step).
  • the separation part is formed of an insulating material and easily repels the liquid composition (polymerization liquid) for electrolytic polymerization. Therefore, in the porous part near the separation part, it is difficult to highly fill the voids with conductive polymer.
  • the polymerization conditions of electrolytic polymerization in particular, the polymerization voltage
  • the precoating conditions, etc. it is possible to highly fill the conductive polymer in the void even near the separation part, and the filling of the region C rate can be increased. Therefore, the intrusion of air into the capacitor element is suppressed, and the deterioration of the conductive polymer is suppressed, so that it can be used for long periods of time with voltage applied, or when used at high temperatures. Decrease in capacity can be suppressed. Therefore, excellent durability of the solid electrolytic capacitor can be ensured.
  • a solid electrolytic capacitor includes at least one capacitor element.
  • the solid electrolytic capacitor may be of a wound type, a chip type, or a laminated type.
  • a solid electrolytic capacitor may include two or more stacked capacitor elements.
  • the solid electrolytic capacitor may include two or more wound capacitor elements.
  • the configuration of the capacitor element may be selected depending on the type of solid electrolytic capacitor.
  • one end of the cathode lead terminal is electrically connected to the cathode extraction layer.
  • the cathode lead terminal is bonded to the cathode extraction layer by applying a conductive adhesive to the cathode extraction layer.
  • one end of an anode lead terminal is electrically connected to the anode portion of the anode body.
  • the other end of the anode lead terminal and the other end of the cathode lead terminal are each pulled out from the resin exterior body or case.
  • the other end of each terminal exposed from the resin exterior body or case is used for solder connection to a board on which the solid electrolytic capacitor is mounted.
  • the capacitor element is sealed using a resin exterior body or case.
  • the material resin for the capacitor element and the exterior body e.g., uncured thermosetting resin and filler
  • the capacitor element is sealed with the resin exterior body by transfer molding, compression molding, etc. It's okay.
  • the other end portions of the anode lead terminal and the cathode lead terminal connected to the anode lead pulled out from the capacitor element are exposed from the mold.
  • the capacitor element is housed in a bottomed case so that the other end portions of the anode lead terminal and the cathode lead terminal are located on the opening side of the bottomed case, and the opening of the bottomed case is sealed with a sealing body.
  • a solid electrolytic capacitor may be formed by doing so.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a solid electrolytic capacitor according to an embodiment of the present disclosure.
  • the solid electrolytic capacitor of the present disclosure is not limited to the following embodiments. Further, the constituent elements of the following embodiments may be arbitrarily combined with at least one of the above (1) to (4) related to the solid electrolytic capacitor of the present disclosure.
  • a solid electrolytic capacitor 1 includes a capacitor element 2, a resin casing 3 that seals the capacitor element 2, and an anode lead terminal 4 at least partially exposed to the outside of the resin casing 3. and a cathode lead terminal 5.
  • the anode lead terminal 4 and the cathode lead terminal 5 can be made of metal such as copper or copper alloy, for example.
  • the resin exterior body 3 has an approximately rectangular parallelepiped outer shape, and the solid electrolytic capacitor 1 also has an approximately rectangular parallelepiped outer shape.
  • the capacitor element 2 includes an anode foil 6 made of Al foil, a dielectric layer 7 covering the anode foil 6, and a cathode portion 8 covering the dielectric layer 7.
  • the cathode section 8 includes a conductive polymer layer 9 that covers the dielectric layer 7 and a cathode extraction layer 10 that covers the conductive polymer layer 9.
  • the anode foil 6 has porous portions formed by etching or the like on both surface layers.
  • the conductive polymer layer 9 has an inner layer filled in the voids of the porous portion of the anode foil 6 having the dielectric layer 7 , and an outer layer protruding from the main surface of the anode foil 6 .
  • the anode foil 6 includes a region facing the cathode portion 8 (second portion) and a region not facing the cathode portion 8 (first portion).
  • the first portion includes one end (first end) of the anode foil 6 in the length direction, and the second portion includes a second end opposite to the first end.
  • a separation part 13 is formed between the first end and the second end of the anode foil 6 to insulate the first part and the cathode part 8.
  • the separating portion 13 is formed to cover the surface of the anode foil 6 in a band shape, and restricts contact between the cathode portion 8 and the first portion of the anode foil 6 . In the vicinity of the end B on the second end side of the separation section 13, the filling rate in a predetermined region of the porous section is 46% or more.
  • the portion (anode portion) on the first end side is electrically connected to the anode lead terminal 4 by welding.
  • the cathode lead terminal 5 is electrically connected to the cathode portion 8 via an adhesive layer 14 formed of a conductive adhesive.
  • the second part (cathode forming part) including the second end of the anode foil is immersed in a chemical solution, and a DC voltage of 70V is applied for 20 minutes to form a dielectric layer containing aluminum oxide. Formed a body layer.
  • a polymerization solution containing pyrrole (conjugated polymer monomer), naphthalenesulfonic acid (dopant), and water was prepared. Electrolytic polymerization was performed using the obtained polymerization solution in a three-electrode manner. More specifically, a precoated anode foil, a counter electrode, and a reference electrode (silver/silver chloride reference electrode) were immersed in the polymerization solution. A voltage was applied to the anode foil so that the potential of the anode foil with respect to the reference electrode became the polymerization voltage value shown in Table 1, and electrolytic polymerization was performed at 25° C. to form a conductive polymer layer.
  • a silver paste containing silver particles and a binder resin is applied to the surface of the first layer, and the binder resin is cured by heating at 150 to 200°C for 10 to 60 minutes, and the second layer ( A metal particle-containing layer) was formed.
  • a cathode extraction layer consisting of a first layer (carbon layer) and a second layer (metal particle-containing layer) was formed, and a cathode section consisting of a conductive polymer layer and a cathode extraction layer was formed.
  • a capacitor element was produced as described above.
  • the solid electrolytic capacitor was left standing at 145° C. for 400 hours with a voltage of 2 V applied thereto.
  • the capacitance is measured in a 20° C. environment using the same procedure as the initial capacitance, and the average value (C 1 ) of the 20 solid electrolytic capacitors is determined.
  • the C 1 /C 0 ratio is determined, and solid electrolytic capacitors with C 1 /C 0 ⁇ 0.8 are considered defective products with low durability (reliability), and the ratio (%) of the number of defective products out of 20 is determined. Evaluate durability (reliability).
  • the evaluation results are shown in Table 1.
  • A1 to A3 are examples, and B1 to B2 are comparative examples.
  • the solid electrolytic capacitor of the present disclosure can be used in various applications requiring excellent durability (reliability) or high heat resistance.
  • the uses of solid electrolytic capacitors are not limited to these only.
  • Solid electrolytic capacitor 2 Capacitor element 3: Resin casing 4: Anode lead terminal 5: Cathode lead terminal 6: Anode foil 7: Dielectric layer 8: Cathode part 9: Conductive polymer layer (solid electrolyte layer) 10: Cathode extraction layer 11: First layer (carbon layer) 12: Second layer (metal particle containing layer) 13: Separation part 14: Adhesive layer

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  • Electrochemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007281268A (ja) * 2006-04-10 2007-10-25 Nichicon Corp 固体電解コンデンサおよびその製造方法
JP2018129437A (ja) * 2017-02-09 2018-08-16 株式会社村田製作所 固体電解コンデンサ、及び、固体電解コンデンサの製造方法
WO2022044939A1 (ja) * 2020-08-28 2022-03-03 パナソニックＩｐマネジメント株式会社 固体電解コンデンサ素子および固体電解コンデンサ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007281268A (ja) * 2006-04-10 2007-10-25 Nichicon Corp 固体電解コンデンサおよびその製造方法
JP2018129437A (ja) * 2017-02-09 2018-08-16 株式会社村田製作所 固体電解コンデンサ、及び、固体電解コンデンサの製造方法
WO2022044939A1 (ja) * 2020-08-28 2022-03-03 パナソニックＩｐマネジメント株式会社 固体電解コンデンサ素子および固体電解コンデンサ

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