JP5052746B2 - Electrolytic capacitor - Google Patents

Description

  The present invention relates to an electrolytic capacitor used in various electronic devices.

  With the increase in the frequency of electronic devices, there is a demand for a large-capacity electrolytic capacitor that is excellent in equivalent series resistance (hereinafter referred to as ESR) characteristics in the high-frequency region even in an electrolytic capacitor that is an electronic component. Recently, in order to reduce ESR in such a high frequency region, a solid electrolytic capacitor using a solid electrolyte such as a conductive polymer having a higher electric conductivity than a conventional driving electrolyte has been studied and commercialized. Has been. Also, in response to the demand for larger capacity, a wound solid that has a configuration in which a conductive polymer is filled in a capacitor element wound with a separator interposed between an anode foil and a cathode foil Electrolytic capacitors have been commercialized.

  The conductive polymer used in the above solid electrolyte is represented by a method of polymerizing 3,4-ethylenedioxythiophene with ferric p-toluenesulfonate, and the cation component utilizes a metal ion reduction reaction. 3,4-ethylenedioxythiophene chemically oxidized by an oxidant / dopant agent acting as a dopant and a second chloride chloride which also acts as an oxidant / dopant agent using pyrrole monomer. Polypyrrole chemically oxidized and polymerized with iron or persulfate is known.

  However, since the solid electrolytic capacitor as described above uses only a solid electrolyte having a poor dielectric oxide film repair property as an electrolyte, the leakage current is increased as compared with an electrolytic capacitor using a conventional driving electrolytic solution. As a result, short circuit failures due to the occurrence of defects in the dielectric oxide film and dielectric oxide films are likely to occur, making it difficult to construct a capacitor with a high withstand voltage.

  On the other hand, for the purpose of improving the above problems, a wound electrolytic capacitor has been proposed in which both a solid electrolyte made of a conductive polymer and a driving electrolyte are used as a cathode lead material. This wound electrolytic capacitor is made conductive with a separator polymer such as manila paper or kraft paper, or a porous polymer or synthetic fiber nonwoven fabric separator with a conductive polymer that has been chemically oxidized and polymerized as a persulfate, an oxidizing agent and a dopant. It is configured using a conductive separator and a driving electrolyte.

As prior art document information related to the invention of this application, for example, the following patent documents 1 and 2 are known.
JP-A 64-090517 Japanese Patent Application Laid-Open No. 07-249543

  However, a wound electrolytic capacitor using both the above-described conventional solid electrolyte composed of a conductive polymer and a driving electrolyte as a cathode lead material has characteristics even with a driving electrolyte used in combination with a conductive separator. It changes a lot. In particular, the acid component that functions as a dopant can be easily dedoped and eluted into the driving electrolyte solution, or the conductivity of the conductive polymer can be significantly reduced by dedoping, thereby improving the thermal stability of the electrolytic capacitor. There is a problem that the ESR change with time in the high frequency region is poor.

  As a countermeasure against the above-mentioned dedoping, dedoping can be reduced by selecting a doping material, but the material is expensive and the manufacturing conditions of the conductive polymer are difficult.

  An object of the present invention is to solve such a conventional problem and to provide a highly reliable electrolytic capacitor having a low ESR in a high frequency region.

In order to achieve the above object, the present invention provides conductivity by attaching a conductive polymer between an anode foil having a roughened surface and a dielectric oxide film and a cathode foil having a roughened surface. A capacitor element configured by winding with the provided conductive separator interposed therebetween, and a bottomed cylindrical metal case containing the capacitor element together with a driving electrolyte composed of an organic solvent, a solute, and an additive, In the electrolytic capacitor comprising a sealing member sealing the opening of the metal case, the solute is composed of an acid component material and a base component material, and the acid component material includes an organic carboxylic acid and an inorganic acid, The organic carboxylic acid is at least one of phthalic acid, trimellitic acid, pyromellitic acid, maleic acid, salicylic acid, benzoic acid, and resorcinic acid, and the inorganic acid includes boric acid, hypophosphorous acid, Lid sulfone acid, fluoroboric acid, phosphoric acid, Ru der either ethyl phosphate ester, or rag diglycolic acid is a complex compound materials organic and inorganic acids of the acid component, in either borodisalicylate acid In addition , the dopant as the acid contained in the conductive separator is obtained by making the material of the base component a tertiary amine and making the acid component of the solute excessive in molar ratio with respect to the base component of the solute. In this configuration, de-doping is suppressed in the driving electrolyte.

  As described above, the electrolytic capacitor according to the present invention has a configuration in which the molar ratio of the acid component and the base component, which are solute components in the driving electrolyte solution, is acid-excess, and thus the acid of the dopant contained in the conductive separator. Since the component and the acid component in the driving electrolyte solution are kept in an equilibrium state, dedoping of the conductive separator can be suppressed. As a result, it is possible to obtain a highly reliable electrolytic capacitor having a low ESR in a high frequency region.

  Furthermore, by containing an antioxidant in the additive, it is possible to suppress the oxidative deterioration of the conductive separator and to suppress the decrease in electrical conductivity, thereby providing a highly reliable electrolytic capacitor with low ESR in the high frequency range. It becomes possible to do. When the antioxidant is used in combination with an acid, the reaction activity is increased and the effect is further improved.

  FIG. 1 is a partially cutaway perspective view showing a configuration of an electrolytic capacitor according to an embodiment of the present invention. In FIG. 1, reference numeral 19 denotes a capacitor element. The capacitor element 19 has an anode foil 11 made of an aluminum foil having a dielectric oxide film formed by anodizing after the surface is roughened by etching, and a surface by etching. The cathode foil 12 made of a roughened aluminum foil is wound with a conductive separator 13 covered with a conductive polymer interposed therebetween.

  14 and 15 are anode leads and cathode leads for external lead connected to the anode foil 11 and the cathode foil 12, respectively, and 17 is a bottomed cylindrical aluminum housing the capacitor element 19 together with a driving electrolyte (not shown). A metal case 16 having a hole through which the anode lead 14 and the cathode lead 15 are inserted to seal the opening of the metal case 17, and 18 having a hole through which the anode lead 14 and the cathode lead 15 are inserted. It is an insulating seat plate made of an insulating resin mounted on the lever sealing member 16 side. A surface mount type electrolytic capacitor is formed by bending the anode lead 14 and the cathode lead 15 along a groove provided on the outer surface of the insulating seat plate 18.

  The driving electrolyte solution includes an organic solvent, a solute, and an additive, and the acid component of the solute includes an organic acid and an inorganic acid, and the acid component is contained in excess in a molar ratio with respect to the base component. .

  Examples of the organic solvent include alcohols [methanol, ethanol, propanol, butanol, cyclobutanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, methyl cellosolve, ethyl cellosolve, methoxypropylene glycol] and the like. Examples of the aprotic organic solvent include amides [N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, etc. ], Lactones [γ-butyrolactone, β-butyrolactone, α-valerolactone, γ-valerolactone, etc.], sulfoxides [sulfolane, 3-methylsulfolane, dimethyl sulfoxide], cyclic amides [ethylene carbonate, propylene carbonate, etc.] Nitrile [acetonitrile etc.], oxide [dimethyl sulfoxide etc.], imidazolidinone [3-methyl-1,3-oxazolidine-2-one, 1,3-diethyl-2-imidazolidinone, 1, 3-dipropyl-2-imidazolidinone, 1 Methyl-3-ethyl-2-imidazolidinone, 1,3,4-trimethyl-2-imidazolidinone, a 1,3,4,5-tetramethyl-2-imidazolidinone, etc.].

  These organic solvents can be used alone or in combination.

  Polycarboxylic acid and monocarboxylic acid can be used as the organic acid as the acid component of the solute of the driving electrolyte.

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids: ([saturated polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1, 6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid], [unsaturated polycarboxylic acid, such as maleic acid, fumaric acid, icotanic acid]), aromatic polycarboxylic acid: (for example, phthalic acid, isophthalic acid, terephthalic acid , Trimellitic acid, pyromellitic acid), alicyclic polycarboxylic acid: (for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, etc.).

  Examples of the monocarboxylic acid include aliphatic monocarboxylic acids (having 1 to 30 carbon atoms): ([saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, capryl. Acid, pelargonic acid, lauric acid, myristic acid, stearic acid, behenic acid], [unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, oleic acid]), aromatic monocarboxylic acids: (eg benzoic acid, cinnamon) Acid, naphthoic acid), oxycarboxylic acid: (for example, salicylic acid, mandelic acid, resorcinic acid). Among these, maleic acid, phthalic acid, benzoic acid, pyromellitic are preferable because of their high conductivity and thermal stability. Acid, resorcinic acid.

  Examples of the inorganic acid as the acid component of the solute of the driving electrolyte include carbon compounds, hydrogen compounds, boron compounds, sulfur compounds, nitrogen compounds, and phosphorus compounds. Examples of typical inorganic acids include phosphoric acid, phosphorous acid, hypophosphorous acid, alkyl phosphoric acid ester, boric acid, borofluoric acid, tetrafluoroboric acid, hexafluorophosphoric acid, benzenesulfonic acid, naphthalenesulfonic acid Etc.

  Moreover, the complex compound of an organic acid and an inorganic acid can be used as an acid component. For example, borodiglycolic acid, borodisuccinic acid, borodisalicylic acid and the like can be mentioned.

  The base component of the solute of the driving electrolyte is a compound having an alkyl-substituted amidine group, and examples thereof include imidazole compounds, benzimidazole compounds, and alicyclic amidine compounds (pyrimidine compounds and imidazoline compounds). Specifically, 1,8-diazabicyclo [5,4,0] undecene-7,1,5-diazabicyclo [4,3,0] nonene-, which can provide a capacitor having high conductivity and excellent impedance performance 5,1,2-dimethylimidazolinium, 1,2,4-trimethylimidazoline, 1-methyl-2-ethyl-imidazoline, 1,4-dimethyl-2-ethylimidazoline, 1-methyl-2-heptylimidazoline, 1-methyl-2- (3′heptyl) imidazoline, 1-methyl-2-dodecylimidazoline, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-methylimidazole, 1-methylbenzimidazole preferable.

  Further, a quaternary salt of a compound having an alkyl-substituted amidine group can be used as a base component, and an imidazole compound, a benzimidazole compound, or an alicyclic quaternized with an alkyl group having 1 to 11 carbon atoms or an arylalkyl group. Examples include amidine compounds (pyrimidine compounds and imidazoline compounds). Specifically, 1-methyl-1,8-diazabicyclo [5,4,0] undecene-7, 1-methyl-1,5-diazabicyclo [, which can provide a capacitor having high conductivity and excellent impedance performance. 4,3,0] nonene-5, 1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,2-dimethyl-3-ethyl-imidazolinium, 1 , 3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethyl-2-heptylimidazolinium, 1,3-dimethyl-2- (3′heptyl) imidazolinium, 1,3-dimethyl- 2-dodecylimidazolinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1,3-dimethylimidazolium, 1-methyl-3-ethylimidazole Um, 1,3-dimethyl-benzo imidazolium are preferred.

  Tertiary amine can also be used as a base component, and trialkylamines (trimethylamine, dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, dimethylisopropylamine, methylethyl n-propylamine, methylethylisopropylamine) , Diethyl n-propylamine, diethylisopropylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, etc., phenyl group-containing amine (dimethylphenylamine, methylethylphenylamine, diethylphenylamine) Of these, trialkylamines having a high electrical conductivity are preferred, and trimethylamine, dialkylamine having a high electrical conductivity are more preferred. Methyl ethyl amine, is intended to include one or more selected from diethylamine, the group consisting of triethylamine.

  The content of the solute in the driving electrolyte solution of the present invention is usually 10 to 95% by weight, preferably 20 to 90% by weight, based on the weight of the driving electrolyte solution. Outside this range, the conductivity is significantly reduced.

  Examples of additives for the driving electrolyte of the present invention include phosphorus compounds (such as phosphate esters), boric acid compounds (boric acid, complex compounds of boric acid and polysaccharides [mannit, sorbit, etc.]), boron Complex compounds of acids and polyhydric alcohols (ethylene glycol, glycerin, etc.), nitro compounds (o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-nitrophenol, m-nitrophenol, p- Nitrophenol, etc.). Adding these additives may increase the spark voltage of the driving electrolyte and may be preferable.

  Further, the additive can contain an antioxidant, and examples of the antioxidant include phenol compounds, amine compounds, azo compounds, silane compounds, quinone compounds, carboxylic acid compounds, phenol, methylphenol, ethylphenol. , Pyrogallol, hydroquinone, pyrocatechol, tocophenol, butylhydroxyanisole, dibutylhydroxytoluene, benzoquinone, naphthoquinone, anthraquinone, citric acid, ascorbic acid, ethylenediaminetetraacetic acid, quinic acid, rutin, flavonoids, γ-oryzanol, tocophenolbenzotriazole 2,6-di-t-butyl-p-cresol, stearyl propionate-β- (3,5-di-t-butyl-4-hydroxyphenyl), 2,2′-methylene-bis (3-methyl -6 t-butylphenol), dilaurylthiodipropinate, triphenyl phosphite, diphenylisodecyl phosphite, tris (nonylphenyl) phosphite, trisnonylphenyl phosphite, hydroxyanisole, 1,4-naphthalenediol, Examples include trimethylhydroquinone, 2,3-dimethylhydroquinone, aminohydroquinone, and aminophenol.

  Hereinafter, specific examples will be described.

(Examples 3, 4, 6, 8, 9, 11, Reference Examples 1 to 5 and Comparative Examples 1 to 2)
First, a separator base material (base material thickness 50 μm, weighing 25 g / m ² ) made of a nonwoven fabric obtained by a spunbond method using an aromatic polyamide resin mainly composed of polyparaphenylene terephthalamide as a raw material, It was immersed in a mixed solvent of water and ethanol containing ammonium persulfate (concentration 3% by weight) and organic acid, 2-naphthalenesulfonic acid (concentration 5% by weight). The impregnation amount of the oxidizing agent solution at this time was 15 mg / cm ² . This separator is placed on a tank containing a pyrrole monomer, kept in an airtight state at 40 ° C., left for 5 minutes, taken out, washed in warm water at 60 ° C. for 5 minutes, and then dried at 105 ° C. As a result, a conductive separator was obtained. As a result of measuring the conductivity of this conductive separator, it was 2 S / cm.

  Next, an anode foil made of an aluminum foil having a dielectric oxide film (formed voltage 10 V) formed by roughening the surface by etching and then anodizing, and a cathode foil obtained by etching the aluminum foil are electrically conductive. A capacitor element was produced by winding with a conductive separator interposed.

  Subsequently, this capacitor element was immersed in each driving electrolyte shown in (Table 1) under reduced pressure conditions (−700 mmHg), and the driving electrolyte was impregnated in the gap of the capacitor element.

  Next, this capacitor element is formed into a bottomed cylindrical shape together with a resin vulcanized butyl rubber sealing material (composed of 30 parts of butyl rubber polymer, 20 parts of carbon and 50 parts of inorganic filler, sealing body hardness: 70 IRHD [international rubber hardness unit]). After being inserted into the aluminum case, the opening of the aluminum case is sealed by curling treatment, and both lead terminals derived from the anode foil and the cathode foil are passed through an insulating seat plate made of polyphenylene sulfide, and the lead portion is flattened. The insulating seat plate was fixed by bending.

  Finally, aging was performed by continuously applying a DC voltage of 6.3 V for 1 h (atmosphere temperature: 105 ° C.) to produce surface mount type electrolytic capacitors (size: diameter 10 mm × height 10 mm).

With respect to the electrolytic capacitors of Examples 3, 4, 6, 8, 9, 11, Reference Examples 1 to 5 and Comparative Examples 1 and 2, the electrical characteristics after the initial state and the 105 ° C. load test were measured ( Table 2).

As apparent from (Table 2), the electrolytic capacitors of Examples 3 and 4 and Reference Examples 1 and 2 were obtained by making the acid component of the solute in the driving electrolyte more excessive than the molar ratio of the base component. Since the dopant, which is an acid contained in the conductive separator, has an effect of suppressing dedoping in the driving electrolyte, the ESR in the high frequency region is lower than that of Comparative Example 1, and the electrolysis is highly reliable. A capacitor can be obtained.

In addition, the electrolytic capacitors of Examples 6, 8, 9 and Reference Examples 3 and 4 were prepared by using pyromellitic acid, trimellitic acid, benzoic acid as the organic acid of the acid component used in Examples 3 and 4 and Reference Examples 1 and 2 , respectively. Acid, mixed with resorcinic acid, and those using a driving electrolyte containing antioxidants using hypophosphorous acid, naphthalenesulfonic acid, borofluoric acid, phosphoric acid, ethyl phosphate as inorganic acids However, the characteristics are superior to those of Comparative Example 2, and the same characteristics as those of the electrolytic capacitors of Examples 3 and 4 can be obtained.
Further, the electrolytic capacitors of Example 11 and Reference Example 5 using a compound compound of an organic acid and an inorganic acid as the solute acid component can also obtain the same characteristics as the electrolytic capacitors of Examples 6 , 8 , and 9 .

  Although the chip type electrolytic capacitor is used in the above embodiment, it goes without saying that the same effect can be obtained with an electrolytic capacitor that does not use an insulating seat plate.

  The electrolytic capacitor according to the present invention has a special effect that the electric conductivity of the conductive polymer constituting the conductive separator does not deteriorate due to the driving electrolyte used in combination with the conductive separator. It is useful for applications where it is desired to efficiently reduce ESR in a high frequency region and to exhibit stable performance over a long period of time.

1 is a partially cutaway perspective view showing a configuration of an electrolytic capacitor according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Anode foil 12 Cathode foil 13 Conductive separator 14 Anode lead 15 Cathode lead 16 Sealing member 17 Metal case 18 Insulating seat 19 Capacitor element

Claims (1)

Winding an anode foil with a roughened surface and a dielectric oxide film, and a cathode foil with a roughened surface, with a conductive separator added between them to attach a conductive polymer. A capacitor element constituted by the above, a bottomed cylindrical metal case containing the capacitor element together with a driving electrolyte composed of an organic solvent, a solute, and an additive, and a seal that seals the opening of the metal case In the electrolytic capacitor comprising a member, the solute includes an acid component material and a base component material, and the acid component material includes an organic carboxylic acid and an inorganic acid, and the organic carboxylic acid includes phthalic acid, trimellitic acid, It is at least one of pyromellitic acid, maleic acid, salicylic acid, benzoic acid, resorcinic acid, and the inorganic acid is boric acid, hypophosphorous acid, naphthalenesulfonic acid, borofluoric acid, Phosphate, Ru der either ethyl phosphoric acid ester, or rag diglycolic acid is a complex compound materials organic and inorganic acids of the acid component, with either a borodisalicylate acid, of the base component materials Is a tertiary amine, and the dopant that is an acid contained in the conductive separator is dedoped into the driving electrolyte by making the acid component of the solute excessive in molar ratio with respect to the base component of the solute. An electrolytic capacitor designed to suppress this.

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