JP3037704B2 - Electrolyte for electrolytic capacitors - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an improvement in an electrolytic solution for an electrolytic capacitor, and more specifically, to an electrolytic capacitor having improved withstand voltage by adding a specific additive. The present invention relates to an improvement in an electrolytic solution for an electrolytic capacitor which can be performed.

[Prior Art] Electrolytic capacitors are small, large-capacity, inexpensive, and have excellent characteristics such as smoothing of rectified output, and are one of the important components of various electric and electronic devices. An aluminum film converted into an oxide film by oxidation is used as an anode, and this oxide film is used as a dielectric material and an electrolytic solution is interposed between the current collector and the collector. During use, the oxide film is constantly regenerated, so that the oxide film is stable.

Since the electrolytic capacitor is used while performing a chemical reaction, its characteristics greatly depend on the properties of the electrolytic solution. It is important to maintain the steady state of the chemical reaction between the aluminum electrode with the oxide film on the surface and the electrolytic solution and the aluminum oxide film as the dielectric to stabilize the performance. If the chemical steady state is disturbed by, for example, an excessively high voltage load or the like by mistake in the method, the aluminum oxide film is destroyed, and eventually the insulation is broken.

In a chemical reaction that proceeds during use of the electrolytic capacitor, the electrolyte forms an ionic conductor that is a medium for ion transfer. At the interface between the electrolyte and the electrode, the charge moves due to the progress of the electrolytic reaction, the oxidation reaction progresses on the anode surface, the reduction reaction progresses on the cathode surface, and ions move along with the electrolyte in the electrolyte, which is the ion conductor. Electric current flows. Therefore, the electric conductivity of the electrolytic solution reflects the characteristics of the electrolytic solution, which is an ion conductor, in a chemical reaction that proceeds during use of the electrolytic capacitor, and is one of important indicators for evaluating the overall performance of the capacitor.

A phenomenon in which the electrochemical state fluctuates as a result of a change in the physical properties of a dielectric material due to an increase in the load voltage of a capacitor and a high voltage load resulting in a temporal change in dielectric constant is called scintillation. Can be used as a scintillation voltage (withstand voltage) as a measure of the withstand voltage of the capacitor, and the scintillation voltage (withstand voltage)
The higher the value, the higher the withstand voltage of the capacitor. The withstand voltage can be simply measured without assembling a final capacitor product in a state where an unformed aluminum foil of an appropriate size is immersed in the electrolytic solution to be measured.

Since the capacitance of the capacitor is proportional to the dielectric constant of the dielectric, a dielectric having a high dielectric constant should be used, and the dielectric constant should be kept high during use to avoid physicochemical changes of the dielectric. The tangent of the loss angle, that is, the dielectric loss tangent, which is the difference between the phase of the charging current and the phase of the external electric field, is used as a measure of the power consumption of the capacitor. A small value indicates that the power consumption is small. The leakage current, which is the current flowing when the charge reaches a certain value after the start of charging, is due to the steady movement of the charge carrier in the dielectric, and the ions generated by the dissociation of impurities in the dielectric form the charge carrier. It is believed that the magnitude of the change in leakage current reflects the stability of the electrochemical state of the dielectric.

In the conventional general electrolytic solution for electrolytic capacitors,
An acid such as boric acid or a salt thereof is added to the electrolyte as a main solute in order to obtain a high withstand voltage. Attempts have also been made to improve the electrolytic solution for electrolytic capacitors to obtain high withstand voltage by adding various additives other than these.

Examples of additives for obtaining high withstand voltage include addition of sulfamic acid (JP-A-49-82963), addition of suberic acid (JP-A-49-133860), and addition of dodecyl phosphate (JP-A-49-133860). JP-A-49-73659), addition of alkyl phosphoric acid (JP-A-52-153154), addition of hypophosphorous acid (JP-A-57-14)
No. 1913) and the use of a boric acid-mannitol-polyvinyl alcohol system (Japanese Patent Application Laid-Open No. 59-177915) have been proposed, but improvement in withstand voltage while maintaining high conductivity has not always been sufficiently expected. .

[Problems to be Solved by the Invention] The present invention relates to an electrolytic solution for an electrolytic capacitor, which has an improved withstand voltage while maintaining good characteristics of the electrolytic solution for an electrolytic capacitor and provides stable characteristics even when used for a long time at a high temperature. The purpose is to provide.

[Means for Solving the Problems] According to the present invention, in an electrolytic solution for driving an aluminum electrolytic capacitor, an electrolytic solution containing an organic polar solvent as a main solvent and an organic acid or an inorganic acid or a salt thereof as a solute is used. R—O— (CH ₂ CH ₂ O) _n —H (wherein n is an integer of 1 or more, and R is an aliphatic hydrocarbon group in a higher alcohol residue having a total of 6 or more carbon atoms) Wherein a polyoxyethylene alkyl (alkenyl) ether having the formula: is added. In the formula, n is preferably about 1 to 100.

Polyoxyethylene alkyl (alkenyl) of the present invention
Specific examples of the higher alcohol portion (alkyl (alkenyl) group) of the ether include the following higher alcohols: higher alcohol hexyl alcohol, heptyl alcohol, octyl alcohol, caprylic alcohol, nonyl alcohol,
Decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol, merisyl alcohol, oleyl alcohol, and Higher alcohols such as phytol. The higher alcohol is a general term for alcohols having 6 or more carbon atoms.

Specific examples of the solvent that can be used alone or in combination with the organic polar solvent of the electrolytic solution include the following solvents: Protic polar solvent: ethanol, propanol, butanol, pentanol, hexanol, cyclobutanol, cyclobutane Pentanol, cyclohexanol, and monohydric alcohols such as benzyl alcohol, ethylene glycol, propylene glycol, glycerin, methoxyethanol, ethoxyethanol, methoxypropylene glycol, dimethoxypropanol,
Polyhydric alcohols and alcohol ethers such as methylcellosolve and ethylcellosolve, aprotic polar solvent N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methyl Acetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, and amide solvents such as hexamethylphosphoric amide, γ-butyrolactone, N-methyl-2-pyrrolidone,
Lactones such as ethylene carbonate, propylene carbonate and isobutylene carbonate; cyclic amide solvents; nitrile solvents such as acetonitrile; and oxide solvents such as dimethyl sulfoxide.

Specific examples of electrolytes that can be used alone or in combination for the electrolyte of the organic or inorganic acid or its salt electrolyte include the following electrolytes: organic acids formic acid, acetic acid, propionic acid, enanthic acid, etc. Of aliphatic monocarboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, methylmalonic acid, pimelic acid, suberic acid, azelaic acid,
Aliphatic dicarboxylic acids such as sebacic acid, decanedicarboxylic acid, maleic acid, citraconic acid, and itaconic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, salicylic acid, toluic acid, and pyromellitic acid; inorganic acids boric acid; and phosphorus acid, silicic acid, HBF _4, inorganic acids, ammonium ammonium such as HPF ₆ (NH ₄ ^+), methylammonium, ethylammonium, and mono-alkyl ammonium, such as propyl ammonium, dimethyl ammonium, diethyl ammonium, methyl ammonium, and dibutyl Dialkyl ammonium such as ammonium, trimethyl ammonium, triethyl ammonium,
Also, trialkylammonium such as tributylammonium, tetramethylammonium, triethylmethylammonium, tributylammonium, tetraethylammonium, and quaternary ammonium such as N, N-dimethylpyrrolidinium, and other phosphonium and arsonium can be used.

The organic polar solvent of the electrolytic solution for an electrolytic capacitor according to the present invention may be the protic polar solvent alone, but preferably the protic polar solvent is 0 to 50 parts by weight and the aprotic polar solvent is 100 to 50 parts by weight. And prepared by mixing. If necessary, about 0 to 30 parts by weight of water can be mixed. It is preferable to dissolve 1 to 30 parts by weight of an organic or inorganic acid or a salt thereof as a solute in such a solvent system.

The polyoxyethylene alkyl (alkenyl) ether is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 5 parts by weight based on the solute-solvent electrolyte.
By adding parts by weight, it is possible to provide an electrolytic solution for an electrolytic capacitor that can realize high withstand voltage while maintaining good capacitor characteristics.

[Function] A polyoxyethylene alkyl (alkenyl) ether having a unique structure to be added to the electrolytic solution for an electrolytic capacitor disclosed in the present invention comprises an organic polar solvent as a main solvent, and an organic acid or an inorganic acid or a salt thereof as a solute. The action mechanism itself is not clear what action it takes in the electrolyte solution. However, the electrolytic solution for an electrolytic capacitor according to the present invention has some contribution to stabilization of a chemical steady state of an electrochemical reaction system composed of an anode, a cathode, an aluminum oxide film dielectric and an electrolytic solution of an electrolytic capacitor. It is estimated that there is.

As described above, since the electrolytic capacitor is used while performing a chemical reaction, its characteristics greatly depend on the properties of the electrolytic solution. It is important for the stabilization of the performance to maintain the steady state of the chemical reaction occurring between the aluminum electrode having the oxide film on the surface and the electrolyte and the aluminum oxide film serving as the dielectric in good condition.

The present invention provides a polyoxyethylene alkyl (alkenyl) ether having a unique structure by adding
The surface active action of the additive protects the oxide film from hydration degradation and provides good capacitor characteristics.

[Effects of the Invention] According to the present invention, there is provided an electrolytic solution for an electrolytic capacitor which has an improved withstand voltage while maintaining good characteristics of the electrolytic solution for an electrolytic capacitor and which has stable characteristics even when used for a long time at a high temperature. Is done.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited only to the following examples.

Composition of electrolytic solution As shown below, using an organic polar solvent as a main solvent,
Water was added as required, and solutes and polyoxyethylene alkyl (alkenyl) ether were added to prepare electrolytic solutions for electrolytic capacitors according to the present invention (Examples 1 to 8). Controls (Comparative Examples 1 to 8) each having the same composition except that no polyoxyethylene alkyl (alkenyl) ether was added were also prepared. Each composition is given in parts by weight in parentheses.

The polyoxyethylene alkyl (alkenyl) ether used in the above-mentioned general formula is polyoxyethylene stearyl ether (n = 30) indicated by A, and polyoxyethylene tridecyl ether (n = 20)
Are indicated by B, those of polyoxyethylene oleyl ether (n = 15) are indicated by C, and those of polyoxyethylene cetyl ether (n = 60) are indicated by D.

Example 1 and Comparative Example 1 Solvent: ethylene glycol (80) water (7) methylcellosolve (20) solute: diammonium adipate (20) adipic acid (3) polyoxyethylene alkyl (alkenyl) ether: A (3 ) (Example 1 only).

Example 2 and Comparative Example 2 Solvent: Ethylene glycol (100) Water (5) Solute: Ammonium benzoate (15) Polyoxyethylene alkyl (alkenyl) ether: A (2) (Example 2 only).

Example 3 and Comparative Example 3 Solvent: Ethylene glycol (100) Water (7) Solute: Ammonium sebacate (17) Polyoxyethylene alkyl (alkenyl) ether: B (3) (Example 3 only).

Example 4 and Comparative Example 4 Solvent: γ-butyrolactone (60) Methylcellosolve (15) Ethylene glycol (10) Solute: Monotetramethylammonium phthalate (15) Boric acid (2) Mannit (2) Polyoxyethylene Alkyl (alkenyl) ether: C (3) (Example 4 only).

Example 5 and Comparative Example 5 Solvent: γ-butyrolactone (60) Methylcellosolve (15) Ethylene glycol (10) Solute: Tetraethylammonium benzoate (15) Boric acid (2) Mannit (2) Polyoxyethylene alkyl ( Alkenyl) ether: C (4) (Example 5 only).

Example 6 and Comparative Example 6 Solvent: γ-butyrolactone (60) Ethylene glycol (20) Solute: Monotriethylammonium maleate (20) Boric acid (2) Mannit (2) Polyoxyethylene alkyl (alkenyl) ether: D (3) (Example 6 only).

Example 7 and Comparative Example 7 Solvent: N, N-dimethylformamide (60) Ethylene glycol (20) Solute: Monotriethylammonium maleate (20) Polyoxyethylene alkyl (alkenyl) ether: D (3) (Example 7) only).

Example 8 and Comparative Example 8 Solvent: N, N-dimethylformamide (65) Ethylene glycol (20) Solute: Tetramethylammonium benzoate (15) Polyoxyethylene alkyl (alkenyl) ether: C (4) (Example 8) only).

Conductivity and Withstand Voltage of Electrolyte Solution The conductivity and withstand voltage at 30 ° C. of the electrolyte solutions of Examples 1 to 8 and Comparative Examples 1 to 8 are shown in Table 1. Although the addition of polyoxyethylene alkyl (alkenyl) ether tended to slightly lower the electrical conductivity, the withstand voltage was greatly improved. Table 1 Conductivity (ms / cm) Withstand voltage (V) Example 1 4.30 220 Comparative example 1 4.95 150 Example 2 4.04 345 Comparative example 4.44 250 Example 3 4.01 440 Comparative example 3 4.59 350 Example 4 7.90 95 Comparative Example 4 8.62 85 Example 5 5.54 130 Comparative Example 5 6.45 90 Example 6 7.41 120 Comparative Example 6 7.81 100 Example 7 11.5 115 Comparative Example 7 13.3 75 Example 8 8.11 120 Comparative Example 8 8.93 75

Claims (1)

(57) [Claims] 1. An electrolytic solution for driving an aluminum electrolytic capacitor, which comprises an organic polar solvent as a main solvent and an organic acid or an inorganic acid or a salt thereof as a solute, having the following general formula: R--O-(CH during ₂ CH ₂ O) _n -H (wherein, n is an integer of 1 or more, polyoxyethylene alkyl R is having an aliphatic hydrocarbon group) in the total carbon number of 6 or more higher alcohol residues ( An electrolytic solution for an electrolytic capacitor, comprising alkenyl) ether.