CN100419928C - Electrolyte for electrolytic capacitor - Google Patents
Electrolyte for electrolytic capacitor Download PDFInfo
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- CN100419928C CN100419928C CNB031374204A CN03137420A CN100419928C CN 100419928 C CN100419928 C CN 100419928C CN B031374204 A CNB031374204 A CN B031374204A CN 03137420 A CN03137420 A CN 03137420A CN 100419928 C CN100419928 C CN 100419928C
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02B—HYDRAULIC ENGINEERING
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D2600/00—Miscellaneous
- E02D2600/20—Miscellaneous comprising details of connection between elements
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
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Abstract
An electrolyte for electrolytic condenser with high conductivity is provided. First, an electrolyte that an electrolyte salt consisted of a quaternary ammonium cation and a carboxylic acid anion is solved in an organic solution, wherein the sum of the weight percent base on the weight of the electrolyte for a decomposer by adding water of the organic solution is below 2%. Second, an electrolyte that an electrolyte salt consisted of a quaternary ammonium cation and a carboxylic acid anion is solved in a organic solution, wherein the sum of the weight percent base on the weight of the electrolyte for a tertiary amine commensurate to the quaternary ammonium cation and a tertiary ammonium salt is below 1 %. Third, an electrolyte that an electrolyte salt consisted of a quaternary ammonium cation and a carboxylic acid anion is solved in an organic solution, wherein the sum of the weight percent base on the weight of the electrolyte for an ester from the carboxylic acid anion is below 2%.
Description
Technical field
The present invention is about a kind of electrolyte that uses in electrolytic capacitor.
Background technology
In recent years, for the purpose of the Low ESRization of electrolytic capacitor, the electrolyte of a kind of high conductivity of an urgent demand.To this requirement, the electrolyte (for example with reference to patent documentation 1) that originally to propose to have 4 grades of ammonium salts with the aromatic carboxylic acid be solute, with the scheme of 4 grades of ammonium salts of 4 grades of ammonium salts of maleic acid, citraconic acid electrolyte (for example with reference to patent documentation 2) that is solute.
[patent documentation 1]
The open 1991-8092 communique (the 1st page) of Japan Patent
[patent documentation 2]
The open 1991-6646 communique (the 1st page) of Japan Patent
But the conductivity of these electrolyte is usually insufficient.Purpose of the present invention just provides a kind of electrolyte for electrolytic capacitor of high conductivity.
Summary of the invention
Present inventors have carried out research with keen determination in order to solve above-mentioned problem, found that the inadequate reason of this conductivity is owing to contain impurity in electrolyte, promptly 1. from the solvent of the impurity of solvent add the water decomposition material, 2. from 3 grades of amine of the impurity of electrolytical cation constituent and 3 grades of ammonium salts, 3. from the ester of the impurity of electrolytical anion component each, and can improve conductivity by reducing its content.
So, first, electrolyte for electrolytic capacitor of the present invention, it is characterized in that: in a kind of at least a kind of organic solvent (B) of in the group who is formed by gamma-butyrolacton, 3-methyl-2-oxazolidine and 2-pyrrolidines, selecting, make the electrolyte of electrolytic salt (A) dissolving that is made of 4 grades of ammonium cations (a1) and carboxylate anion (a2), the total weight containing ratio based on the weight of electrolyte that adds water decomposition thing (C) of the organic solvent shown in wherein following general expression (1), (2) and (3) is below 2%;
Second, electrolyte for electrolytic capacitor of the present invention, it is characterized in that: a kind of electrolyte that in organic solvent (E), makes electrolytic salt (G) dissolving that is constituted by 4 grades of ammonium cations (g1) and carboxylate anion (g2), the total weight containing ratio based on the weight of electrolyte that wherein comes from 3 grades of amine (j1) of these 4 grades of ammonium cations (g1) and 3 grades of ammonium salts (j2) is below 1%;
The 3rd, electrolyte for electrolytic capacitor of the present invention, it is characterized in that: the total weight containing ratio based on the weight of electrolyte that a kind of electrolyte that at least a kind of carboxylate anion (m2) of selecting and 4 grades of ammonium cations (m1) form among the group who is made up of O-phthalic acid anion, maleic acid anion and citraconic acid anion electrolytic salt (M) is dissolved in organic solvent (L), wherein following general expression (4), (5) reach the ester (N) shown in (6) is below 2%.
Embodiment
At first describe about the 1st invention.
The relevant total amount that adds water decomposition material (C) from the solvent of the impurity of the solvent of electrolyte based on electrolyte weight of the present invention is generally below the 2 weight %.Add the occasion of water decomposition material containing this that surpass 2 weight %, conductivity is low.The amount that in the electrolyte this adds the water decomposition material is preferably below 1% weight, is more preferred from below the 0.5 weight %.
As (C), can enumerate in solvent the occasion of using gamma-butyrolacton by the material hydroxy-iso-butyric acid shown in the above-mentioned general expression (1) [following note is made (C1)], in solvent, use 3-methyl-2-oxazolidine occasion by the material N-ethoxy shown in the above-mentioned general expression (2)-N-methylamino formic acid [following note is made (C2)] and the occasion of in solvent, using the 2-pyrrolidines by the material 4-aminobutyric acid shown in the above-mentioned general expression (3) [following note is made (C3)].
Employed solvent (B) is at least a kind of selection from the group who is made up of gamma-butyrolacton, 3-methyl-2-oxazolidine and 2-pyrrolidines in the electrolyte of the present invention, the electrolyte that uses these solvents is because the conductivity height, can suppress to wave the dried expansion (dry up) of the electrolyte that looses and cause by the evaporation of solvent, and the serviceability temperature scope is wide, so used by glad.These solvents have each ester bond, urethane bond and amido link, so be subjected to the occasion of thermo-lag under the situation that has moisture to exist, added water decomposition and generate and add water decomposition thing (C) shown in above-mentioned.Therefore be that principal component is dissolved in the electrolyte of solute and also can be contained (C) with these solvents.
The content that adds water decomposition thing (C) given to this invention can by for example nulcear magnetic resonance (NMR) absorption analysis (
1H-NMR) and quantitatively.Will
1H etc. have the atomic nucleus of magnetic moment and put into magnetic field, produce nulcear magnetic resonance (NMR) when giving the electromagnetic field of appropriate frequency, and absorb its electromagnetic energy.The position of the chemical shift that can absorb from the nulcear magnetic resonance (NMR) that is observed, the intensity of resonance absorption are constructed and quantitative opinion.
Add in the water decomposition thing (C),, electrolyte is being diluted by heavy DMSO (Dimethyl sulfoxide, dimethyl sulfoxide (DMSO)) and using the nulcear magnetic resonance (NMR) absorption analysis device under 300MHz, to implement by shown in the above-mentioned general expression (1)
1When H-NMR analyzes ,～3.5ppm～the position show the characteristic peaks of 2 protons.By shown in the above-mentioned general expression (2), similarly implementing
1When H-NMR analyzes ,～3.8ppm～the position show the characteristic peaks of 2 protons.By shown in the above-mentioned general expression (3), similarly implementing
1When H-NMR analyzes ,～2.7ppm～the position show the characteristic peaks of 2 protons.By the standard substance that in electrolyte, adds known quantity, and with standard substance
1The H-NMR peak integration than and above-mentioned general expression (1), (2), (3)
1H-NMR integration ratio compares, can quantitative above-mentioned general expression (1), the amount of (2), (3).Can enumerate chloroform, benzene etc. as standard substance, be good with chloroform.
Be reduced to the following method of 2 weight % as amount with (C) in the electrolyte, for example can enumerate 1. by silica gel, active carbon, activated alumina, specific molecule sieve etc. the method for adsorption treatment (C), 2. under the situation of heating electrolyte, make the method for moisture below 0.2 weight % that become the essential factor that adds water decomposition by carrying out decompression dehydration, 3. adjust the method for the acid/alkali balance of electrolyte.Owing to (C) particularly promoted,, be preferably 1 so can be 1: 1～1: 1.05 by 4 grades of ammonium cations (a1) that make formation electrolytic salt (A) and carboxylate anion's (b1) molar ratio in alkali its generation of zone; 1～1: 1.02, electrolyte is become faintly acid and suppresses its generation from neutrality.In method 1., can make by adsorption treatment to add water decomposition thing (C) and be reduced to which kind of level, depend on the kind and the treatment conditions of used adsorbent.In method 2., for the accessory substance of the impurity that suppresses other, temperature, decompression degree etc. imposes a condition and becomes important.So in the method 3. owing to there be not other the accessory substance and the possibility of sneaking into of impurity preferable.1., 2., method 3. both can be carried out also capable of being combined carrying out respectively separately.
As the used 4 grades of ammonium cations (a1) of the present invention, can enumerate for example following kind.
1. 4 grades of ammoniums of aliphat
Tetramethylammonium, ethyl trimethyl ammonium, methyl triethyl ammonium, etamon, diethyl-dimethyl ammonium, tetrapropyl ammonium, TBuA etc.
2. alicyclic 4 grades of ammoniums
N, N-dimethyl pyrrolidine, N, N-diethyl pyrrolidines, N-methyl-N-ethyl pyrrolidine, N, N-picoline, N-ethylpyridines etc. such as N-lupetidine, N, N-diethyl piperidines
3. 4 grades of ammoniums of aromatics
N-picoline, N-ethylpyridine etc.
As carboxylic acid that go up to pay protonation the used carboxylate anion of the present invention (a2) (a2 '), can enumerate for example following kind.
Monocarboxylic acid { aliphat monocarboxylic acid [saturated monocarboxylic acid (the formic acid of C1～30, acetate, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, dodecylic acid, tetradecanoic acid, octadecanoid acid, 22 (carbon) alkanoic acid etc.) and unsaturated monocarboxylic acid (acrylic acid, methacrylic acid, and one dollar aromatic carboxylic acid's [benzoic acid oleic acid etc.)], cinnamic acid, naphthoic acid etc.] } and polycarboxylic acids (polycarboxylic acids of 2～4 valencys) { aliphatic polycarboxylic acid's [saturated polycarboxylic acids (ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid etc.); Unsaturated polyester carboxylic acid (maleic acid, citraconic acid, fumaric acid, itaconic acid etc.)]; Aromatics polycarboxylic acids [phthalic acid, M-phthalic acid, terephthalic acid (TPA), trimellitic acid, Pyromellitic Acid etc.]; Aliphat hydroxy acid [glycolic acid, lactic acid, tartaric acid etc.]; Aromatics hydroxy acid [salicylic acid, mandelic acid etc.]; Sulfur-bearing polycarboxylic acids [sulphur support propionic acid] and other polycarboxylic acids [cyclobutane-1,2-dicarboxylic acids, cyclopentene-1,2-dicarboxylic acids, furans-2,3-dicarboxylic acids, two rings [2,2,1] heptane-2-alkene-2,3-dicarboxylic acids, two rings [2,2,1] seven-2-alkene-2,3-dicarboxylic acids], two rings [2,2,1] seven-2,5-diene-2,3-dicarboxylic acids etc. }
These the insides are conductivity height, excellent maleic acid and the citraconic acid of solvent solubility preferably, also has conductivity height, heat-staple aromatic monocarboxylate, aromatics polycarboxylic acids, aromatics hydroxy acid etc.
As electrolytic salt of the present invention (A), can enumerate for example following kind.
Phthalic acid list tetramethylammonium, maleic acid list tetramethylammonium, citraconic acid list tetramethylammonium, phthalic acid list ethyl trimethyl ammonium, maleic acid list ethyl trimethyl ammonium, citraconic acid list ethyl trimethyl ammonium, phthalic acid list N, the N-dimethyl pyrrolidine, maleic acid list N, the N-dimethyl pyrrolidine, citraconic acid list N, the N-dimethyl pyrrolidine, phthalic acid list N, N-diethyl pyrrolidines, maleic acid list N, N-diethyl pyrrolidines, citraconic acid list N, N-diethyl pyrrolidines, phthalic acid list N-picoline, maleic acid list N-picoline, citraconic acid list N-picoline etc.
The content of the electrolytic salt in the electrolyte of the present invention (A), viewpoint from electric conductivity, weight based on electrolyte, be preferably more than 5% weight, be more preferred from more than the 10 weight %, viewpoint to the solubility of electrolyte solvent is preferably below the 70 weight %, is more preferred from below the 40 weight %.
In electrolyte of the present invention, as required, can add the solvent of for example from following group, selecting more than a kind as secondary solvent (B ').The addition of secondary solvent (B ') be to more than the 0 weight % of electrolyte total weight below the 50 weight %.
1. ethanol class
1 valency ethanol: 1 valency ethanol (benzyl ethyl alcohol, octanol etc.) more than 7 of 1 valency ethanol of carbon number 1～6 (methyl ethanol, ethyl hexanol, propyl group ethanol, butyl alcohol, diacetone ethanol, furfuryl group ethanol etc.), carbon number,
Divalent ethanol: divalent ethanol (ethohexadiol etc.) more than 7 of the divalent ethanol of carbon number 1～6 (ethylene glycol, propylene glycol, two ethylene glycol, hexylene glycol etc.), carbon number,
3 valency ethanol: 3 valency ethanol (propylene glycol etc.) of carbon number 1～6,
From 4 valencys to 6 valencys or the ethanol more than it: carbon number 1～6 from 4 valencys to 6 valencys or the ethanol more than it (hexitol).
2. ethers
Monoether (glycol monomethyl methyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, TC, glycol monomethyl phenyl ether, oxolane, 3 monomethyl oxolanes etc.), diether (ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether etc.) etc.
3. amide-type
Benzamide type (N-methylformamide, N, dinethylformamide, N-ethyl-formamide, N, N-diethylformamide etc.), ethanamide (N-methylacetamide, N, N-dimethylacetylamide, N-ethyl acetamide, N, N-diethyl acetamide etc.), Propionamides (N, N-dimethyl propylene acid amides, hexamethyl phosphoramide etc.), oxazole alkanes (3,5-dimethyl-2-oxazolidine etc.).
4. lactone
α-acetyl-gamma-butyrolacton, beta-butyrolactone, gamma-valerolactone, δ-Wu Neizhi etc.
5. nitrile
Acetonitrile, acrylonitrile etc.
6. carbonic ester
Ethylene carbonate, propylene carbonate etc.
7. other organic polar solvent
N-crassitude, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidine etc.
Preferably sulfolane, ethylene glycol in the above-mentioned secondary solvent (B ').
In electrolyte of the present invention, can add common used all additives (D) in the electrolyte as required.As this additive (D), can enumerate for example phosphoric acid derivatives (for example phosphoric acid, phosphate etc.), boronic acid derivatives (for example complex compound of complex compound, boric acid and the multivalence ethanol [ethylene glycol, glycerol etc.] of boric acid, boric acid and polysaccharide [mannitol, D-sorbite etc.] etc.), nitro compound (for example o-nitrobenzoic acid, p-nitrobenzoic acid, m-nitrobenzoic acid, o-nitrophenol, p-nitrophenol etc.) etc.(D) total addition is that electrolyte is added up to below the 10 weight % of weight for good.
Then, describe about the 2nd invention.
The total amount based on the weight of electrolyte of 3 grades of amine (j1) of the impurity of relevant electrolyte cation constituent from electrolyte of the present invention and 3 grades of ammonium salts (j2) is below 1% weight.Containing above 1 weight % (j1) and occasion (j2), conductivity is low.(j1) amount that reaches (j2) is preferably below the 0.5 weight %, is more preferred from below the 0.2 weight %.
Reach (j2) as (j1), can enumerate for example following kind.
1. 3 grades of amine of aliphat and 3 grades of ammonium salts
3 grades of amine of aliphat: Trimethylamine, ethyl dimethyl amine, methyl diethylamide, triethylamine, three-n-propylamine, tri-n-butylamine, diethyl-i-propylamine etc.
3 grades of ammonium salts of aliphat: phthalic acid list leptodactyline, maleic acid list leptodactyline, citraconic acid list leptodactyline, maleic acid list ethyl dimethyl ammonium, phthalic acid list ethyl dimethyl ammonium, citraconic acid list ethyl dimethyl ammonium, citraconic acid monomethyl diethyl ammonium salt, phthalic acid monomethyl diethyl ammonium salt, maleic acid monomethyl diethyl ammonium salt, phthalic acid list triethyl ammonium salt, maleic acid list triethyl ammonium salt, citraconic acid list triethyl ammonium salt, phthalic acid list three-n-third ammonium salt, maleic acid list three-n-third ammonium salt, citraconic acid list three-n-third ammonium salt, phthalic acid Dan Sanding ammonium salt, maleic acid Dan Sanding ammonium salt, citraconic acid Dan Sanding ammonium salt, phthalic acid list diethyl-i-third ammonium salt, maleic acid list diethyl-i-third ammonium salt, citraconic acid list diethyl-i-third ammonium salt etc.
2. 3 grades of amine of ester ring type and 3 grades of ammonium salts
3 grades of amine of ester ring type: N-crassitude, N-ethyl pyrrolidine, N-methyl piperidine, N-ethylpiperidine etc.
3 grades of ammonium salts of ester ring type: phthalic acid list N-crassitude, maleic acid list N-crassitude, citraconic acid list N-crassitude, phthalic acid list N-ethyl pyrrolidine, maleic acid list N-ethyl pyrrolidine, citraconic acid list N-ethyl pyrrolidine, phthalic acid list N-methyl piperidine, maleic acid list N-methyl piperidine, citraconic acid list N-methyl piperidine, phthalic acid list N-ethylpiperidine, maleic acid list N-ethylpiperidine, citraconic acid list N-ethylpiperidine etc.
3. 3 grades of amine of aromatics and 3 grades of ammonium salts
3 grades of amine of aromatics: pyridine etc.
3 grades of ammonium salts of aromatics: phthalic acid list pyridine, maleic acid list pyridine, citraconic acid list pyridine etc.
(j1) given to this invention and total amount (j2) can be by for example liquid chromatograph quantitatively.In advance by (j1) of concentration known and mobile phase solution (j2) and carry out carrying out quantitatively according to the method for deciding by the internal standard method after liquid chromatograph measures and make calibration curve.
As the representative manufacture method of 4 grades of ammonium salts of electrolytic salt of the present invention (G), in organic solvent (j1), make the carbonic diester reaction and after 4 grades of changes, make acid reaction, the method etc. of carrying out decarbonate, desolventizing after a while is known.When 4 grades of changes of (j1) are insufficient, in electrolyte, can sneak into (j1) and reach (j2).
In order to reduce (j1) and (j2) in the electrolyte, for example can enumerate 1. when changing reactions, do one's utmost to improve by 4 grades of 3 grades of amine of carbonic diester the method for its conversion ratio, 2. stay down by 4 grades of ammonium salts are under reduced pressure heated lift the method for 3 residual amine, 3. by with 4 grades of ammonium salts crystallization and the method etc. of removing 3 grades of ammonium salts again.In method 1., in order to do one's utmost fully to transform, the setting of the reaction condition of material molar ratio, solvent, temperature, pressure, time etc. becomes important.And the carrying out of conversion can be confirmed by utilizing liquid chromatograph to react tracking.In method 2., in order to suppress the accessory substance of other impurity,, temperature, decompression degree etc. become important so imposing a condition.Carry out in method 3. when the crystallization again, conditions such as the employed solvent types of crystallization, amount, partial crystallization temperature, number of times become important again.1., 2., method 3. both can carry out separately, also can make up and carry out.
As electrolytic salt of the present invention (G), can enumerate for example above-mentioned electrolytic salt of lifting (A).
As the used organic solvent of the present invention (E), can enumerate for example above-mentioned organic solvent of lifting (B).And organic solvent (E) can add up to weight to add the above-mentioned secondary solvent of lifting below the 50 weight % more than the 0 weight % (B ') to electrolyte as required.
As organic solvent (E), be preferably gamma-butyrolacton, 3-methyl-2-oxazolidine, 2-pyrrolidines.
As the 4 grades of ammonium salts (g1) that are equivalent to 3 grades of amine of the present invention and 3 grades of ammonium salts, can enumerate the illustrated kind of for example above-mentioned conduct (a1).
As carboxylate anion of the present invention (g2), can enumerate the illustrated kind of for example above-mentioned conduct (a2).
The content of the electrolytic salt of electrolyte of the present invention (G), viewpoint from electric conductivity, be preferably more than the 5 weight % based on the weight of electrolyte, be more preferred from more than the 10 weight %, from viewpoint to the solubility of electrolyte solvent, be preferably below the 70 weight %, be more preferred from below the 40 weight %.
In electrolyte of the present invention, can add as required electrolyte normally used all additives (K).As this additive (K), can enumerate the illustrated kind of above-mentioned conduct (D).(K) total amount is good below the 10 weight % that electrolyte added up to weight.
Then describe about the 3rd invention.
The ester (N) of the impurity of relevant electrolytic anion composition from electrolyte of the present invention, be the ester shown in the above-mentioned general expression (4), phthalic acid monomethyl ester (N1), ester shown in the above-mentioned general expression (5), maleic acid monomethyl ester (N2), and the total amount based on the weight of electrolyte of ester, the citraconic acid monomethyl ester (N3) shown in the above-mentioned general expression (6), below 2% weight.In the occasion of amount above 2 weight %, conductivity is low.Amount is preferably below the 1 weight %, is more preferred from below the 0.5 weight %.
Representative manufacture method as 4 grades of ammonium salts of electrolytic salt of the present invention (M), have in alcohol solvent, make and in 3 grades of amine, make the carbonic diester reaction and the material of 4 grades of changes, in the material that anhydrous phthalic acid and/or anhydrous maleic acid and/or anhydrous citraconic acid is added water decomposition with water, react, dewater after a while, the method for decarbonate, desolventizing.
Anhydrous phthalic acid and/or anhydrous maleic acid and/or anhydrous citraconic acid add the inadequate occasion of water decomposition, they have residual in electrolyte.The ethanol of residual anhydrous phthalic acid and/or anhydrous maleic acid and/or anhydrous citraconic acid and reaction dissolvent etc. reacts, and generates the ester (N) of above-mentioned general expression (4), (5) and (6).
The content of ester given to this invention can by for example nulcear magnetic resonance (NMR) absorption analysis (
1H-NMR) and quantitatively.
(N) any all can use nulcear magnetic resonance (NMR) absorption analysis device to implement with 300MHz with heavy DMSO dilute electrolyte
1When H-NMR analyzes ,～3.8ppm～the position show the characteristic peaks of 3 protons.By the standard substance that in electrolyte, adds known quantity and with standard substance
1H-NMR peak integration ratio and above-mentioned (N's)
1H-NMR peak integration ratio compares, amount that can quantitatively above-mentioned (N).As standard substance, can enumerate chloroform, benzene etc., be preferably chloroform.
In order to reduce (N) in the electrolyte, for example can enumerate 1. anhydrous phthalic acid, anhydrous maleic acid and anhydrous citraconic acid add water decomposition the time do one's utmost to improve the method for its conversion ratio, 2. by with the crystallization and remove method of residual impurity etc. again of 4 grades of ammonium salts.Make conversion ratio bring up to which kind of level in method 1., the selected of reaction condition of the mol ratio of water and sour anhydride, temperature, time etc. is important.When carrying out crystallization again in method 2., conditions such as the employed solvent types of crystallization, amount, partial crystallization temperature, number of times are important again.1., method 2. both can be carried out also capable of being combined carrying out separately.
As 4 grades of ammonium cations used in the present invention (m1), can enumerate the illustrated kind of above-mentioned conduct (a1).
As electrolytic salt of the present invention (M), can enumerate for example above-mentioned electrolytic salt of lifting (A).
As organic solvent used in the present invention (L), can enumerate for example above-mentioned organic solvent of lifting (B).And organic solvent (L) can be as required, adds electrolyte is added up to the above-mentioned secondary solvent of lifting below the 50 weight % more than the 0 weight % of weight (B ').
As organic solvent (L), be preferably gamma-butyrolacton, 3-methyl-2-oxazolidine, 2-pyrrolidines.
The content of the electrolytic salt of electrolyte of the present invention (M), viewpoint from electric conductivity, be preferably more than the 5 weight % based on the weight of electrolyte, be more preferred from more than the 10 weight %, from viewpoint to the solubility of electrolyte solvent, be preferably below the 70 weight %, be more preferred from below the 40 weight %.
In electrolyte of the present invention, can add as required electrolyte normally used all additives (P).As this additive (P), can enumerate the illustrated kind of above-mentioned conduct (D).(P) total amount is good below the 10 weight % that electrolyte added up to weight.
The electrolyte of the present invention the 1st, the 2nd and the 3rd invention can be used in the electrolytic capacitor.
Then describe, but the present invention is not limited thereto about specific embodiment of the present invention.
The modulation of＜electrolyte 〉
Embodiment 1
Pack in the 1L autoclave methyl alcohol 67.3g and dimethyl carbonate 66.2g (0.74 mole) are warming up to 120 ℃ under airtight.Then depress adding, be blown into Trimethylamine 41.4g (0.7 mole) with 10 hours and carry out 4 grades of change reactions.4 grades of change conversion ratios of reactant liquor are 92.6%.Afterwards, temperature is brought up to 135 ℃ ,-face continues reaction again by liquid chromatograph tracking reaction one side reaches more than 99.9% 4 grades of change conversion ratios, and obtains the methanol solution 174.9g of tetramethyl-ammonium-methylcarbonate.
In 4 mouthfuls of flasks of 1L, pack into anhydrous phthalic acid 108.8g (0.74 mole) and excessive ion exchange water 189.0g (10.5 moles), under 95 ℃, carry out 2 hours add the water decomposition reaction.
1The result that H-NMR analyzes, the water decomposition rate that adds of anhydrous phthalic acid is 99.9%.Then, with 4 hours above-mentioned tetramethyl-ammonium-methylcarbonate 174.9g that drip so that acid/alkali mol ratio becomes 1.05.Drip finish after, reduce pressure subsequently and carry out decarbonate, desolventizing, dehydration with 120 ℃, normal pressure, obtain tetramethyl-ammonium-phthalate 206g.Make salinity become 25 weight % its dilution by the gamma-butyrolacton of selling on the market, and consider the moisture in capacitor, sneak into moisture to be adjusted to 5.5wt%, finish electrolyte from electrolytic paper.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 0.01wt%, and amount (C2) is 0wt%, and amount (C3) is 0wt%, so the total amount that adds water decomposition thing (C) of solvent is 0.01wt%.
And, be 0.03wt% from the total amount of the leptodactyline of the trimethyl of 3 grades of amine of cationic impurity (j1) and 3 grades of ammonium salts (j2).
In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 0wt%, so be 0wt% from the total amount of anionic impurity ester (N).
Embodiment 2
Except making dimethyl carbonate 66.2g (0.74 mole) with anhydrous maleic acid 72.0g (0.74 mole) replacement, modulate electrolyte with N-crassitude 69.4g (0.7 mole) replacement, anhydrous phthalic acid 108.8g (0.74 mole) similarly to Example 1 with diethyl carbonate 86.8g (0.74 mole) replacement, Trimethylamine 41.4g (0.7 mole).In addition, the change of 4 grades behind 4 order reactions under 120 ℃ conversion ratio is 91.6%.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 0.01wt%, and amount (C2) is 0wt%, and amount (C3) is 0wt%, so total amount (C) is 0.01wt%.And, be 0.02wt% from cationic impurity (j1) and total amount (j2).In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 0wt%, so total amount (N) is 0wt%.
Embodiment 3
Except making anhydrous phthalic acid 108.8g (0.74 mole), modulate electrolyte similarly to Example 1 with anhydrous citraconic acid 82.3g (0.74 mole) replacement.In addition, the change of 4 grades behind 4 order reactions under 120 ℃ conversion ratio is 91.4%.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 0.01wt%, and amount (C2) is 0wt%, and amount (C3) is 0wt%, so total amount (C) is 0.01wt%.And, be 0.02wt% from cationic impurity (j1) and total amount (j2).In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 0wt%, so total amount (N) is 0wt%.
Embodiment 4
Except making gamma-butyrolacton, modulate electrolyte similarly to Example 1 with 3-methyl-2-oxazolidine replacement.In addition, 4 grades of conversion ratios behind 4 order reactions under 120 ℃ are 91.4%.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 0wt%, and amount (C2) is 0.01wt%, and amount (C3) is 0wt%, so total amount (C) is 0.01wt%.And, be 0.02wt% from cationic impurity (j1) and total amount (j2).In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 0wt%, so total amount (N) is 0wt%.
Embodiment 5
Except making gamma-butyrolacton, modulate electrolyte similarly to Example 1 with the replacement of 2-pyrrolidines.In addition, 4 grades of conversion ratios behind 4 order reactions under 120 ℃ are 91.5%.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 0wt%, and amount (C2) is 0wt%, and amount (C3) is 0.02wt%, so total amount (C) is 0.02wt%.And, be 0.02wt% from cationic impurity (j1) and total amount (j2).In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 0wt%, so total amount (N) is 0wt%.
Comparative example 1
Except the charge weight that makes anhydrous phthalic acid is that 98.4g (0.67 mole), acid/alkali mol ratio are 0.96, modulate electrolyte similarly to Example 1.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 3.1wt%, and amount (C2) is 0wt%, and amount (C3) is 0wt%, so total amount (C) is 3.1wt%.And, be 0.03wt% from cationic impurity (j1) and total amount (j2).In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 0wt%, so total amount (N) is 0wt%.
Comparative example 2
135 ℃ under, add thermal response again except not being implemented among the embodiment 14 grades when changing reactions, and make gamma-butyrolacton, modulate electrolyte similarly to Example 1 with beyond the replacement of 2-pyrrolidines.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 0.01wt%, and amount (C2) is 0wt%, and amount (C3) is 0wt%, so total amount (C) is 0.01wt%.And, be 1.8wt% from cationic impurity (j1) and total amount (j2).In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 0wt%, so total amount (N) is 0wt%.
Comparative example 3
Except make the anhydrous citraconic acid of embodiment 3 add the water decomposition reaction when, the amount of ion exchange water be 18.9g (1.05 moles) in addition, modulate electrolyte similarly to Example 2.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 0.01wt%, and amount (C2) is 0wt%, and amount (C3) is 0wt%, so total amount (C) is 0.01wt%.And, be 0.02wt% from cationic impurity (j1) and total amount (j2).In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 3.2wt%, so total amount (N) is 3.2wt%.
Comparative example 4
Except the charge weight of the anhydrous phthalic acid that makes embodiment 4 is that 98.4g (0.67 mole), acid/alkali mol ratio are 0.96, modulate electrolyte similarly to Example 4.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 0wt%, and amount (C2) is 2.9wt%, and amount (C3) is 0wt%, so total amount (C) is 2.9wt%.And, be 0.02wt% from cationic impurity (j1) and total amount (j2).In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 0wt%, so total amount (N) is 0wt%.
Comparative example 5
Except the charge weight of the anhydrous phthalic acid that makes embodiment 5 is that 98.4g (0.67 mole), acid/alkali mol ratio are 0.96, modulate electrolyte similarly to Example 5.
1The result that H-NMR analyzes and liquid chromatograph is analyzed, amount (C1) is 0wt%, and amount (C2) is 0wt%, and amount (C3) is 4.0wt%, so total amount (C) is 4.0wt%.And, be 0.02wt% from cationic impurity (j1) and total amount (j2).In addition, amount (N1) is 0wt%, and amount (N2) is 0wt%, and amount (N3) is 0wt%, so total amount (N) is 0wt%.
The amount of the impurity in the electrolyte described in embodiment 1～5 and the comparative example 1～5 is come together in the table 1.
1The condition determination that H-NMR analyzes and liquid chromatograph is analyzed is as follows.
＜
1H-NMR analyzes 〉
Device: nulcear magnetic resonance (NMR) absorption analysis device A-300 (Japanese Bruker society system)
Measure solvent: heavy DMSO
Frequency: 300MHz
＜liquid chromatograph analysis 〉
Device: high-speed liquid chromatography instrument LC-10A (Shimadzu Seisakusho Ltd.'s system)
Cylinder: Capcell PAK (SHISEIDO society system)
Mobile phase: the ion exchange water that contains phosphatase 11 0mM and sodium perchlorate 100mM.
Flow velocity: 0.8ml/min
Sample dilution ratio: carry out 100 times of dilutions by mobile phase
Sample injection rate: 20 μ l
Detector: UVIDEC-100V
Detect wavelength: 210nm
Use the electrolyte of embodiment 1～5 and comparative example 1～5, measure conductivity, its result of expression in table 1.
＜conductivity 〉
Use the system conductivity meter CM-40S of East Asia electric wave Co., Ltd., be determined at 30 ℃ conductivity.
As shown in Table 1, the electrolyte of embodiments of the invention 1～5 is compared with the electrolyte of comparative example 1～5, has good conductivity characteristic.
Electrolyte of the present invention is because the amount that adds water decomposition thing, 3 grades of amine and 3 grades of ammonium salts and ester of the solvent of impurity is few, so conductivity is good.Therefore by using electrolyte of the present invention can seek the high performance of electrolytic capacitor.
Claims (7)
1. electrolyte for electrolytic capacitor, it is characterized in that: at least a kind of organic solvent (B) of in the group who is formed by gamma-butyrolacton, 3-methyl-2-oxazolidine and 2-pyrrolidines, selecting, make the electrolyte of electrolytic salt (A) dissolving that is constituted by 4 grades of ammonium cations (a1) and carboxylate anion (a2), the total weight containing ratio based on the weight of electrolyte that adds water decomposition thing (C) shown in wherein following general expression (1), (2) and (3) is below 2%
2. electrolyte as claimed in claim 1 is characterized in that: above-mentioned carboxylate anion (a2) by maleic acid anion, citraconic acid anion, aromatic carboxylic acid's anion form group in selected at least a kind.
3. electrolyte for electrolytic capacitor, it is characterized in that: make the electrolyte of electrolytic salt (G) dissolving that is made of 4 grades of ammonium cations (g1) and carboxylate anion (g2) in organic solvent (E), the total weight containing ratio based on the weight of electrolyte that wherein comes from 3 grades of amine (j1) of these 4 grades of ammonium cations (g1) and 3 grades of ammonium salts (j2) is below 1%.
4. electrolyte as claimed in claim 3 is characterized in that: above-mentioned organic solvent (E) by gamma-butyrolacton, 3-methyl-2-oxazolidine and 2-pyrrolidines form group in selected at least a kind.
5. as claim 3 or 4 described electrolyte, it is characterized in that: above-mentioned carboxylate anion (g 2) by maleic acid anion, citraconic acid anion, aromatic carboxylic acid's anion form group in selected at least a kind.
6. electrolyte for electrolytic capacitor, it is characterized in that: the electrolyte that at least a kind of carboxylate anion (m2) of selecting and 4 grades of ammonium cations (m1) form among the group who is made up of O-phthalic acid anion, maleic acid anion and citraconic acid anion electrolytic salt (M) is dissolved in organic solvent (L), the total weight containing ratio based on the weight of electrolyte of the ester (N) shown in wherein following general expression (4), (5) and (6) is below 2%
7. electrolyte as claimed in claim 6 is characterized in that: above-mentioned organic solvent (L) by gamma-butyrolacton, 3-methyl-2-oxazolidine and 2-pyrrolidines form group in selected at least a kind.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003098887 | 2003-04-02 | ||
| JP2003098887A JP2004311482A (en) | 2003-04-02 | 2003-04-02 | Electrolytic solution for electrolytic capacitor |
| JP2003-098887 | 2003-04-02 |
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| Publication Number | Publication Date |
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| CN1534701A CN1534701A (en) | 2004-10-06 |
| CN100419928C true CN100419928C (en) | 2008-09-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB031374204A Expired - Fee Related CN100419928C (en) | 2003-04-02 | 2003-06-20 | Electrolyte for electrolytic capacitor |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2004311482A (en) |
| KR (1) | KR100527327B1 (en) |
| CN (1) | CN100419928C (en) |
| TW (1) | TWI220261B (en) |
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| JP5387279B2 (en) * | 2009-09-24 | 2014-01-15 | 日本ケミコン株式会社 | Electrolytic solution for electrolytic capacitors |
| JP6158841B2 (en) * | 2012-12-28 | 2017-07-05 | カーリットホールディングス株式会社 | Electrolytic solution for electrolytic capacitor and electrolytic capacitor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102266A (en) * | 1986-03-24 | 1987-09-30 | 日本凯咪孔株式会社 | Electrolyte for electrolytic capacitor |
| CN1148442A (en) * | 1995-03-02 | 1997-04-23 | 松下电器产业株式会社 | Electrolyte solution for driving electrolytic capacitor and electrolytic capacitor made therewith |
| JPH11233377A (en) * | 1998-02-13 | 1999-08-27 | Matsushita Electric Ind Co Ltd | Electrolytic capacitor drive electrolyte and electrolytic capacitor provided therewith |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930011027A (en) * | 1991-11-22 | 1993-06-23 | 황선두 | Electrolytic solution and electrolytic capacitor using the same |
| KR930014648A (en) * | 1991-12-03 | 1993-07-23 | 황선두 | Non-Aqueous Solution Electrolyte |
| KR940020441A (en) * | 1993-02-26 | 1994-09-16 | 석진철 | Electrolytic Solution for Aluminum Electrolytic Capacitors |
| JPH11214268A (en) * | 1998-01-27 | 1999-08-06 | Matsushita Electric Ind Co Ltd | Electrolyte solution for aluminum electrolytic capacitor and aluminum electrolytic capacitor using the same |
| JPH11340101A (en) * | 1998-05-26 | 1999-12-10 | Tokin Corp | Electrolyte for electric double layer capacitor and electric double layer capacitor |
-
2003
- 2003-04-02 JP JP2003098887A patent/JP2004311482A/en active Pending
- 2003-05-27 TW TW092114231A patent/TWI220261B/en not_active IP Right Cessation
- 2003-06-18 KR KR10-2003-0039376A patent/KR100527327B1/en not_active IP Right Cessation
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102266A (en) * | 1986-03-24 | 1987-09-30 | 日本凯咪孔株式会社 | Electrolyte for electrolytic capacitor |
| CN1148442A (en) * | 1995-03-02 | 1997-04-23 | 松下电器产业株式会社 | Electrolyte solution for driving electrolytic capacitor and electrolytic capacitor made therewith |
| JPH11233377A (en) * | 1998-02-13 | 1999-08-27 | Matsushita Electric Ind Co Ltd | Electrolytic capacitor drive electrolyte and electrolytic capacitor provided therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200421364A (en) | 2004-10-16 |
| KR100527327B1 (en) | 2005-11-09 |
| CN1534701A (en) | 2004-10-06 |
| KR20040086066A (en) | 2004-10-08 |
| JP2004311482A (en) | 2004-11-04 |
| TWI220261B (en) | 2004-08-11 |
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