CN101840785B - Novel electrolyte - Google Patents
Novel electrolyte Download PDFInfo
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- CN101840785B CN101840785B CN2010101545835A CN201010154583A CN101840785B CN 101840785 B CN101840785 B CN 101840785B CN 2010101545835 A CN2010101545835 A CN 2010101545835A CN 201010154583 A CN201010154583 A CN 201010154583A CN 101840785 B CN101840785 B CN 101840785B
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Abstract
The invention discloses a novel electrolyte, which mainly comprises the following components in parts by weight: 30-45 parts of ethylene glycol, 1-5 parts of boric acid, 4-10 parts of at least one kind of long straight-chain saturated dicarboxylic acid or ammonium salt thereof, 40-60 parts of at least one kind of long straight-chain saturated dicarboxylic acid with branched chains or ammonium salt thereof, 2-6 parts of mannitol, 0.1-0.5 part of phosphate and 0.2-0.6 part of dehydrogenation agent. Since the electrolyte uses ethylene glycol as solvent and uses long straight-chain saturated dicarboxylic acid with branched chains, long straight-chain saturated dicarboxylic acid and boric acid as solute, the invention has the advantages that the forming efficiency and the breakdown voltage of the electrolyte are improved, the solubility of the solute is increased, the electric conductivity is improved, the specific resistance is reduced and the service life of the product is improved.
Description
Technical field
The present invention relates to a kind of electrochemical capacitor driving electrolytic solution.
Background technology
Working electrolyte is the actual negative electrode of electrolytic capacitor, and rising provides oxonium ion, repairs the important function of anode oxide film, and therefore, developing high performance Working electrolyte is vital for the performance that guarantees capacitor.Existing electrochemical capacitor driving electrolytic solution is broadly divided into following several types:
1) with ethylene glycol as solvent; With boric acid and boric acid ammonium salt electrolyte as solute; In above-mentioned electrolyte; The esterification that boric acid becomes between metaboric acid and ethylene glycol and the boric acid all can generate condensation water, causes the moisture in the electrolyte too high, and can't use above under 105 ℃ the condition;
2) with ethylene glycol as solvent, with long linear saturated dicarboxylic acid or its salt electrolyte, owing to receive influence of space as solute; The movement velocity of straight chain saturated dicarboxylic acid is little; Solubility is lower, and consequently electrolytic conductivity is on the low side, and easy and crystalline is separated out under cryogenic conditions;
3) with ethylene glycol as solvent; With branched long-chain saturated dicarboxylic acid or its salt electrolyte as solute; Branched long-chain saturated dicarboxylic acid or the solubility of its salt in solvent make moderate progress than the solubility of long linear saturated dicarboxylic acid or its salt, but the formation efficiency of this kind electrolyte and flash over voltage decrease with long linear saturated dicarboxylic acid or its salt electrolyte as solute;
4) a kind of electrolyte is disclosed among the CN1289458C; This kind electrolyte mixes at 8 long-chain biatomic acids more than the carbon atom having alkyl and alkoxy carbonyl and the carbochain between the carboxyl at two ends on 2-methyl azelaic acid and one or more side chains; This kind mixture does not have crystallization to separate out at low temperatures, even at high temperature the conductance deterioration can not take place yet.But above-mentioned preparation cost height with alkyl and alkoxy carbonyl and the carbochain between the carboxyl at two ends causes the production cost of electrolyte to raise;
5) can also use the tricarboxylic acid that has side chain, the flash over voltage of tricarboxylic acid is higher than dicarboxylic acids, but it needs import, costs an arm and a leg.
Summary of the invention
The purpose of this invention is to provide a kind of novel electrolyte; This kind electrolyte with ethylene glycol as solvent, with branched long-chain saturated dicarboxylic acid, long linear saturated dicarboxylic acid and boric acid as solute, on the basis of improving its formation efficiency and diffusing ignition voltage; Strengthen the solubility of solute; Improve conductivity, reduce than resistance, thus the useful life of improving product.
Technical scheme provided by the invention is following:
Novel electrolyte; It is characterized in that it mainly comprises the component of following total amount proportioning: 30～45 parts of ethylene glycol, 1～5 part of boric acid, at least a long linear saturated dicarboxylic acid or 4～10 parts of its ammonium salts, at least a branched long linear saturated dicarboxylic acid or 40～60 parts of its ammonium salts, 2～6 parts in sweet mellow wine, 0.1～0.5 part of phosphate and 0.2～0.6 part of the hydrogen agent that disappears.
In the embodiment that recommends, said long linear saturated dicarboxylic acid can be selected from least a in decanedioic acid, azelaic acid, pimelic acid or the adipic acid.
In the embodiment that recommends; Said branched long linear saturated dicarboxylic acid can be selected from 2-methyl azelaic acid; 3-methyl azelaic acid, 4-methyl azelaic acid, 2,3-dimethyl azelaic acid, 2,4 dimethyl azelaic acids; The isosebacic acid ammonium, at least a in 3-methyl decanedioic acid, 4-methyl decanedioic acid, 2,3-dimethyl decanedioic acid or 2, the 4-dimethyl decanedioic acid etc.
In the embodiment that recommends, said phosphate can be selected from a kind of of diammonium hydrogen phosphate, ammonium hypophosphite or ammonium phosphite, and phosphate is used to suppress the aquation of oxide-film.
In the embodiment that recommends, the described hydrogen agent that disappears can be selected from a kind of in p-nitrophenol, resorcinol, p-nitrophenyl methyl alcohol, paranitrobenzoic acid, ortho-nitroanisole, paranitroanisole or the 1,4-benzoquinone.Preferably, the said hydrogen agent that disappears is a p-nitrophenol, and the p-nitrophenol of above-mentioned weight proportion does not influence the flash over voltage and the conductivity of electrolyte basically, and owing to have inductive effect and conjugation simultaneously, its hydrogen effect that disappears also is superior to other hydrogen agent that disappears.
The component and the weight proportion of a preferred embodiment of the present invention are:
0.4 part of 35.8 parts of ethylene glycol, 2.5 parts of boric acid, 5 parts of decanedioic acid ammonium salts, 2 parts of azelaic acid hydrogen ammonium salts, 50 parts of isosebacic acid ammonium salts, 4 parts in sweet mellow wine, 0.3 part of diammonium hydrogen phosphate salt and p-nitrophenol; This kind electrolyte has higher diffusing ignition voltage, can under the hyperbaric environment of 400V, work.
The component and the weight proportion of another preferred embodiment of the present invention are:
0.4 part of ethylene glycol 44.3,1 part of boric acid, 3 parts of adipic acid ammonium salts, 5 parts of decanedioic acid ammonium salts, 40 parts of isosebacic acid ammonium salts, 2 parts in sweet mellow wine, 0.3 part of diammonium hydrogen phosphate salt, 4 parts of benzoic acid ammonium salts and p-nitrophenol; The diffusing ignition voltage of this kind electrolyte is lower, is used for work under the environment of 250V.
Need to prove that the sweet mellow wine that adds among the present invention is mainly used in the aquation that suppresses oxide-film, improve the high-temperature stability of electrolyte; Boric acid then helps to improve the speed of growth of oxide-film, and has the ability of buffering electrolyte pH fluctuation.
Only if specialize, the implication of employed here all technology and scientific terminology is identical with the affiliated common implication of understanding of one technical staff of technical field of the present invention.Equally, all introduce the present invention as a reference at this publication of mentioning, patent application, patent and other references.
Compared with prior art, the present invention has following characteristics:
1) the present invention selects for use ethylene glycol, boric acid, long linear saturated dicarboxylic acid or its ammonium salt, branched long linear saturated dicarboxylic acid or its ammonium salt, sweet mellow wine, phosphate and the hydrogen agent that disappears etc. as raw material, and it not only obtains easily, and cheap;
2) this kind electrolyte as solvent, as solute, and adds additives such as sweet mellow wine, phosphate and the hydrogen agent that disappears with branched long-chain saturated dicarboxylic acid, long linear saturated dicarboxylic acid and boric acid with ethylene glycol; On the basis of improving its formation efficiency and diffusing ignition voltage, strengthen the solubility of solute, improve conductivity; Reduction is than resistance, thereby improves the useful life of product, improves the speed of growth of oxide-film simultaneously; The aquation that suppresses oxide-film, the high temperature performance of raising electrolyte;
3) branched long-chain saturated dicarboxylic acid content overlength straight chain far away saturated dicarboxylic acid and boric acid are separated out in order to prevent the crystallization under cryogenic conditions of long linear saturated dicarboxylic acid, influence the cryogenic property of electrolyte;
4) boric acid has the effect of regulating pH of buffer.
Embodiment
Below in conjunction with embodiment the present invention is done further description, but do not constitute any restriction of the present invention.
Embodiment
As shown in table 1, the composition of above-mentioned weight proportion is heated to 150 degree while stirring, can obtain electrolyte.
The electrolyte of above-mentioned acquisition is supplied with the thermal degradation when test under the zero load, be about to each electrolyte and under 135 ℃ condition, kept 2000 hours, check 2000 hours later conductivity (ms/cm), moisture content (%) and pH values, result of the test is as shown in table 2.
The boric acid that data from table 2 can be found out, add, long linear saturated dicarboxylic acid or its ammonium salt can improve with branched long linear saturated dicarboxylic acid or its ammonium salt as the electrolyte initial stage conductance of solute and the conductance after the deterioration; In addition; Moisture content after embodiment 1,2,3 and 4 deteriorations raises to some extent; This is that moisture content raises owing between ethylene glycol and binary acid or the boric acid esterification takes place in the deterioration process, and causes the rising of pH value.Compare with comparative example, this phenomenon relaxes in embodiment 1,2,3 and 4 to some extent, and then improves the useful life of product.
The foregoing description is a preferred implementation of the present invention; But execution mode of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. electrolyte; It is characterized in that it mainly comprises the component of following total amount proportioning: 30～45 parts of ethylene glycol, 1～5 part of boric acid, at least a long linear saturated dicarboxylic acid or 4～10 parts of its ammonium salts, at least a branched long linear saturated dicarboxylic acid or 40～60 parts of its ammonium salts, 2～6 parts in sweet mellow wine, 0.1～0.5 part of phosphate and 0.2～0.6 part of the hydrogen agent that disappears.
2. according to the electrolyte described in the claim 1, it is characterized in that: said long linear saturated dicarboxylic acid is selected from least a in decanedioic acid, azelaic acid, pimelic acid or the hexanedioic acid.
3. according to the electrolyte described in the claim 2; It is characterized in that: said branched long linear saturated dicarboxylic acid is selected from 2-methyl azelaic acid; 3-methyl azelaic acid, 4-methyl azelaic acid, 2,3-dimethyl azelaic acid, 2,4 dimethyl azelaic acids; The isosebacic acid ammonium, at least a in 3-methyl decanedioic acid, 4-methyl decanedioic acid, 2,3-dimethyl decanedioic acid or 2, the 4-dimethyl decanedioic acid.
4. according to the electrolyte described in the claim 3, it is characterized in that: said phosphate is selected from a kind of of diammonium hydrogen phosphate, ammonium hypophosphite or ammonium phosphite.
5. according to the electrolyte described in the claim 4, it is characterized in that: the described hydrogen agent that disappears is selected from a kind of in p-nitrophenol, resorcinol, p-nitrophenyl methyl alcohol, paranitrobenzoic acid, ortho-nitroanisole, paranitroanisole or the 1,4-benzoquinone.
6. according to the electrolyte described in the claim 5; It is characterized in that wherein the weight proportion of each raw material is: 0.4 part of 35.8 parts of ethylene glycol, 2.5 parts of boric acid, 5 parts of decanedioic acid ammonium salts, 2 parts of azelaic acid hydrogen ammonium salts, 50 parts of isosebacic acid ammonium salts, 4 parts in sweet mellow wine, 0.3 part of diammonium hydrogen phosphate salt and p-nitrophenol.
7. according to the electrolyte described in the claim 5; It is characterized in that wherein the weight proportion of each raw material is: 0.4 part of ethylene glycol 44.3,1 part of boric acid, 3 parts of hexanedioic acid ammonium salts, 5 parts of decanedioic acid ammonium salts, 40 parts of isosebacic acid ammonium salts, 2 parts in sweet mellow wine, 0.3 part of diammonium hydrogen phosphate salt, 4 parts of benzoic acid ammonium salts and p-nitrophenol.
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| CN2010101545835A CN101840785B (en) | 2010-04-23 | 2010-04-23 | Novel electrolyte |
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| CN2010101545835A CN101840785B (en) | 2010-04-23 | 2010-04-23 | Novel electrolyte |
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| CN101840785B true CN101840785B (en) | 2012-08-22 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013094462A1 (en) * | 2011-12-19 | 2013-06-27 | テイカ株式会社 | Electrolyte capacitor, and method for producing same |
| CN102969161B (en) * | 2012-12-18 | 2016-01-20 | 南通新三能电子有限公司 | The preparation method of aluminium electrolytic capacitor driving electrolytic solution and main solute thereof |
| CN103680982B (en) * | 2013-12-25 | 2017-01-04 | 佛山市高明区利明电子有限公司 | A kind of 250V electrolysis condenser and production technology thereof |
| CN105098235A (en) * | 2014-04-15 | 2015-11-25 | 东莞新能源科技有限公司 | Lithium ion secondary battery and electrolyte thereof |
| CN105575665B (en) * | 2015-12-22 | 2018-08-21 | 东莞市久制电子有限公司 | A kind of high conductance long life aluminum electrolytic capacitor electrolyte and preparation method thereof |
| CN107221438B (en) * | 2017-06-30 | 2019-04-26 | 东莞市久制电子有限公司 | A kind of super-pressure electrolyte solute and preparation method thereof |
| JP7057176B2 (en) * | 2018-03-16 | 2022-04-19 | 日本軽金属株式会社 | Manufacturing method of electrodes for aluminum electrolytic capacitors |
| CN110648850A (en) * | 2019-09-19 | 2020-01-03 | 肇庆绿宝石电子科技股份有限公司 | Aluminum electrolytic capacitor special for high-power supply |
| CN113257575B (en) * | 2021-05-25 | 2022-09-20 | 深圳市凯琦佳科技股份有限公司 | Ultralow-loss electrolyte suitable for 125 degrees and preparation method thereof |
| CN117476368B (en) * | 2023-11-24 | 2024-07-19 | 深圳市东联发科技有限公司 | Aluminum electrolytic capacitor with high stability and long service life |
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| CN1744247A (en) * | 2004-08-30 | 2006-03-08 | 广东风华高新科技股份有限公司 | Aluminium electrolytic capacitor working electrolyte and capacitor obtained thereof |
| CN101114544A (en) * | 2006-07-29 | 2008-01-30 | 广西师范大学 | Working electrolyte for wide temperature high voltage aluminium electrolytic capacitor and method for making same thereof |
| CN101383227A (en) * | 2001-01-15 | 2009-03-11 | 宇部兴产株式会社 | Electrolysis solution for electrolytic capacitors |
| CN101521116A (en) * | 2008-02-28 | 2009-09-02 | 南通瑞达电子材料有限公司 | Working electrolyte of electrolytic capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4517544B2 (en) * | 2001-01-15 | 2010-08-04 | 宇部興産株式会社 | Electrolytic solution for electrolytic capacitor and electrolytic capacitor using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101383227A (en) * | 2001-01-15 | 2009-03-11 | 宇部兴产株式会社 | Electrolysis solution for electrolytic capacitors |
| CN1744247A (en) * | 2004-08-30 | 2006-03-08 | 广东风华高新科技股份有限公司 | Aluminium electrolytic capacitor working electrolyte and capacitor obtained thereof |
| CN101114544A (en) * | 2006-07-29 | 2008-01-30 | 广西师范大学 | Working electrolyte for wide temperature high voltage aluminium electrolytic capacitor and method for making same thereof |
| CN101521116A (en) * | 2008-02-28 | 2009-09-02 | 南通瑞达电子材料有限公司 | Working electrolyte of electrolytic capacitor |
Non-Patent Citations (1)
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