JPS62171109A - Electrolyte for electrolytic capacitor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrolytic solution for an electrolytic capacitor, which contains a fluorocomplex salt of piperidine or piperidine derivatives as an electrolyte in an aprotic solvent.

[Conventional technology]

Conventionally, organic acids or their salts/glycol-based pastes have been mainly used as electrolytes for electrolytic capacitors for normal purposes, but as the scope of use of electronic devices has increased in recent years, there has been a demand for improvements in capacitor performance. As a result, the presence of water in pastes has become a major problem, and electrolytic solutions that use aprotic solvents to replace organic acids or their salts/glycol pastes are attracting attention.

However, the biggest problem with aprotic solvent electrolytes is that
The key is how to obtain an electrolytic solution with high conductivity.
The main search has been for organic carboxylic acids or their salts that have a high degree of dissociation, but there are still solvents that can still achieve that purpose and that still react with acids such as alcohols and glycols to produce water. attempts to obtain high conductivity by blending water with an aprotic solvent, but this method suffers from the drawbacks of not being able to achieve a sufficiently high conductivity, and lack of stability at high temperatures due to increased water content and electrolyte. is the current situation.

Therefore, it is an object of the present invention to provide a substantially non-aqueous highly conductive electrolyte using an aprotic solvent.

[Problem that the invention seeks to solve]

The present inventors have developed a substantially non-aqueous electrolytic solution with high conductivity by using an aprotic solvent and without using a solvent that reacts with acids such as alcohols and glycols to produce water. As a result of intensive research on the electrolytes to be provided, it was discovered that salts of fluorocomplex acids with piperidine or piperidine derivatives have high solubility in aprotic solvents, have a high degree of dissociation, and impart high conductivity. It has been reached.

That is, the electrolytic solution for an electrolytic capacitor according to the present invention has a general formula (where R1 = alkyl substituent having 1 to 6 carbon atoms, n =
0-3. R=I (or an alkyl group having 1 to 5 carbon atoms 1
-2 nitrogen atoms constitute a secondary, tertiary or quaternary amine, and are characterized by containing a fluorocomplex acid salt of piperidine or piperidine derivatives of A=fluorocomplex acid) as an electrolyte.

The piperidine and piperidine derivatives that are the object of the present invention include 2-methylpiperidine; 3-methylpiperidine; 4-methylpiperidine; 1,2-dimethylpiperidine; 1゜4-dimethylpiperidine;
Piperidine; 2.4-dimethylpiperidine; 2.5-
Dimethylpiperidine; 2,6-dimethylbiperidine; 2
．． 3.6-1-tumethylpiperidine. 2.4,61-limethylpiperidine; 2-methyl-5-ethylpiperidine;
2-phenylpiperidine; 3-phenylpiperidine; 4
-Phenylpiperidine; for each N group of the above-mentioned piperidine derivatives, N-methyl, N, N-dimethyl, N-phenylpiperidine;
-Ethyl, N.

N-diethyl, N-n propyl, N, N-di-n-propyl, N-n-butyl, N, N-di-n-butyl, N-isobutyl, N, N-diisobutyl, N-n amyl, N, N-di n? Mil, N-isoamyl, N,N-diisoamyl 4
Examples include piperidine derivatives that have been converted into amine groups.

The aprotic solvents used include: (1) Amide solvents N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide , N-ethylacetamide, N, N-diethylacetamide, hexamethylphosphorinamide.

(2) Oxide-based dimethyl sulfoxide (3) Nitrile-based acetonitrile (4) Representative examples include, but are not limited to, cyclic esters, amide-based γ-butyrolactone, N-methyl-2-pyrrolidone ethylene carbonate, propylene carbonate, etc. It's not something.

The fluorocomplex acids to which the present invention applies include tetrafluoroboric acid (HBF4), hexafluorophosphoric acid (HBF4), and hexafluorophosphoric acid (HBF4).
PF5).

The electrolytic solution for an electrolytic capacitor according to the present invention is generally prepared by adding an equivalent amount of a desired piperidine or piperidine derivatives to an aqueous solution of a fluorocomplex acid, and drying the product under reduced pressure to obtain an anhydrous salt. It can be adjusted to the desired concentration.

〔Example〕

Hereinafter, regarding examples of the electrolytic solution for electrolytic capacitors according to the present invention, conductive dust of a 10% by weight solution of various piperidine-induced fallow fluoro complex salts in various aprotic solvents will be described.
Shown in the table.

As a comparative example, a conventional standard electrolytic solution (78% by weight of ethylene glycol, 12% of water, 10% of ammonium adipate) is shown.

Table 1 Next, 16V for the electrolytes of Examples 1 to 8 and Comparative Examples
The results of the high temperature load test at 1000 μF are shown in Table 2.

Table 2 [Effects of the Invention] According to the electrolytic solution according to the present invention, it is possible to provide a non-aqueous electrolytic solution having a high conductivity comparable to or higher than that of conventional glycols, water, and organic acid salts. This provides the field of electrolytic capacitor design with a new and wide range of performance options.

Claims (3)

[Claims] (1) There are general formulas ▲mathematical formulas, chemical formulas, tables, etc. in the aprotic solvent▼ (In the formula, R_1 = alkyl substituent having 1 to 6 carbon atoms, n
=0 to 3, R=H or an alkyl group having 1 to 5 carbon atoms 1
-2 nitrogen atoms constitute a secondary, tertiary or quaternary amine, A = fluoro complex acid) An electrolytic solution for an electrolytic capacitor containing a fluoro complex acid salt of piperidine or piperidine derivatives as an electrolyte. (2) The aprotic solvent is N-methylformamide, N,
N-dimethylformamide, N-ethylformamide,
N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, γ-butyrolactone, N-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, dimethyl The electrolytic solution for an electrolytic capacitor according to claim 1, which is selected from the group of sulfoxide, acetonitrile, or a mixture thereof. (3) The electrolytic solution for an electrolytic capacitor according to claim 1 or 2, wherein the fluoro complex acid is tetrafluoroboric acid or hexafluorophosphoric acid.