JP2902682B2 - 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, which has been replaced with an oxide film by oxidation, is used as an anode, and this oxide film is used as a dielectric to interpose an electrolytic solution 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 electrode reaction, the oxidation reaction proceeds on the anode surface, the reduction reaction proceeds on the cathode surface, and ions move in the electrolyte solution, 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 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 smaller value indicates that the power consumption is smaller. 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 diacid (JP-A-57-14).
No. 1913), the use of boric acid-mannitol-polyvinyl alcohol system (JP-A-59-177915) has been proposed.
It was not always possible to sufficiently improve the withstand voltage while maintaining high conductivity.

[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. The general formula of: (In the formula, Y ₁ , Y ₂ , and Y ₃ may be the same or different, and each represents — (R ₁ ) ₁ —X, a hydrogen atom, or a higher acyl group, and at least one of them represents a higher acyl group. Also X
Is a hydrogen atom, a higher acyl group or a higher alcohol residue, l is an integer of 1 or more, and R ₁ represents ethylene oxide and / or propylene oxide). An electrolyte solution is provided. Where l is 1 to 100
The degree is preferred.

Specific examples of the fatty acid moiety of the glycerin fatty acid ester of the present invention include the following fatty acids: Saturated fatty acids having the general formula CH ₃ (CH ₂ ) _n COOH (n is an integer of 9 or more): Undecylic acid (n = 9), lauric acid (n = 10), tridecylic acid (n = 11), myristic acid (n = 12), pentadecylic acid (n = 13), palmitic acid (n = 14), heptadecylic acid (N = 15), stearic acid (n = 16), nonadecanoic acid (n = 17), arachiic acid (n
= 18), behenic acid (n = 20), lignoceric acid (n = 2
2), serotonic acid (n = 24), heptacosanoic acid (n = 2
5), montanic acid (n = 27), melicic acid (n = 28),
And unsaturated fatty acids such as lacceric acid (n = 30), unsaturated fatty acids undecylenic acid CH ₂ CHCH (CH ₂ ) ₈ COOH oleic acid C ₁₇ H ₃₃ COOH (cis) <9> elaidic acid C ₁₇ H ₃₃ COOH (trans ) <9> Cetreic acid C ₂₁ H ₄₁ COOH <11> Erucic acid C ₂₁ H ₄₁ COOH (cis) <13> Brassic acid C ₂₁ H ₄₁ COOH (trans) <13> Linoleic acid C ₁₇ H ₃₁ COOH <9, 12> Linolenic acid C ₁₇ H ₂₉ COOH <9,12,15> Arachidonic acid C ₁₉ H ₃₁ COOH <5,8,11,14> Stearolic acid C ₁₇ H ₃₁ COOH <triple bond, 9> (However, <> Indicates the position of the unsaturated bond).

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, quaternary ammoniums such as trialkylammonium such as tributylammonium, tetramethylammonium, triethylmethylammonium, tributylammonium, tetraethylammonium and N, N-dimethylpyrrolidinium, and other phosphoniums and arsoniums 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.

Preferably, the glycerin fatty acid ester described above is added in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 5 parts by weight, to the electrolytic solution comprising such a solute-solvent system, while maintaining good capacitor characteristics. It is possible to provide an electrolytic solution for an electrolytic capacitor that can realize withstand voltage.

[Function] A glycerin fatty acid ester having a unique structure to be added to the electrolytic solution for an electrolytic capacitor disclosed in the present invention is used in 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. It is not clear how it works. 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.

According to the present invention, by adding a glycerin fatty acid ester having a unique structure, the oxide film is protected from hydration deterioration by the surface active action of the additive, and good capacitor characteristics are provided.

[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 necessary, and solutes and glycerin fatty acid esters 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 glycerin fatty acid ester was added were also prepared. Each composition is given in parts by weight in parentheses.

The glycerin fatty acid ester used is represented by A in the above-mentioned general formula, which is dipolyoxyethylene glycerin monostearate (POE = 60),
Dipolyoxyethylene (POE = 20), polyoxypropylene (POP = 15), which is glycerin monooleate is indicated by B, and polyoxypropylene (POP = 30)
Those which are glycerin diundecylenates are indicated by C, those which are monooleyl dipolyoxyethylene glycerin monolaurate (POE = 40) are indicated by D, and those which are glycerin monooleate are E
Indicated by

The chemical structural formulas of the glycerin fatty acid esters A to E used are as follows.

A: Dipolyoxyethylene glycerin monostearate (POE = 60): B; dipolyoxyethylene (POE = 20) polyoxypropylene (POP = 10) glycerin monooleate: C; polyoxypropylene (POP = 30) glycerin diundecylenate: D; monooleic acid dipolyoxyethylene glycerin monolaurate (POE = 40): E; glycerin monooleate: Example 1 and Comparative Example 1 Solvent: ethylene glycol (80) water (7) methylcellosolve (20) solute: diammonium adipate (20) adipic acid (3) glycerin fatty acid ester: A (3) (Example 1) only).

Example 2 and Comparative Example 2 Solvent: Ethylene glycol (100) Water (5) Solute: Ammonium benzoate (15) Glycerin fatty acid ester: A (3) (Example 2 only).

Example 3 and Comparative Example 3 Solvent: Ethylene glycol (100) Water (7) Solute: Ammonium sebacate (17) Glycerin fatty acid ester: B (2) (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) Glycerin fatty acid ester : C (4) (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) Glycerin fatty acid ester: D (3) (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) Glycerin fatty acid ester: E (2) (executed) Example 6 only).

Example 7 and Comparative Example 7 Solvent: N, N-dimethylformamide (60) Ethylene glycol (20) Solute: Monotriethylammonium maleate (20) Glycerin fatty acid ester: D (5) (Example 7 only).

Example 8 and Comparative Example 8 Solvent: N, N-dimethylformamide (65) Ethylene glycol (20) Solute: Tetramethylammonium benzoate (15) Glycerin fatty acid ester: B (3) (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. The addition of glycerin fatty acid ester showed a slight decrease in conductivity, but the withstand voltage was greatly improved.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) H01G 9/035

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. (In the formula, Y ₁ , Y ₂ , and Y ₃ may be the same or different, and each represents — (R ₁ ) ₁ —X, a hydrogen atom, or a higher acyl group, and at least one of them represents a higher acyl group. Also X
Is a hydrogen atom, a higher acyl group or a higher alcohol residue, l is an integer of 1 or more, and R ₁ represents ethylene oxide and / or propylene oxide). Electrolyte.