CN113628885B - Electrolyte for solid-liquid mixed electrolytic capacitor and electrolytic capacitor - Google Patents
Electrolyte for solid-liquid mixed electrolytic capacitor and electrolytic capacitor Download PDFInfo
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- CN113628885B CN113628885B CN202010384426.7A CN202010384426A CN113628885B CN 113628885 B CN113628885 B CN 113628885B CN 202010384426 A CN202010384426 A CN 202010384426A CN 113628885 B CN113628885 B CN 113628885B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/145—Liquid electrolytic capacitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
In order to overcome the problems that the mixed type aluminum electrolytic capacitor in the prior art is not voltage-resistant and the leakage of sealing rubber occurs in the capacitor under the conditions of high temperature and high humidity, the invention provides an electrolyte for a solid-liquid mixed type electrolytic capacitor, which comprises an aprotic solvent, a main solute consisting of imidazolinium cations and organic carboxylic acid anions and a compound A, wherein the compound A has the structure as follows:
R 1 ～R 6 each independently selected from hydrogen atoms or alkyl groups with 1-5 carbon atoms, and the two groups are connected to form a ring or not. The invention also provides an aluminum electrolytic capacitor, which comprises the electrolyte for the solid-liquid mixed type aluminum electrolytic capacitor. When the electrolyte for the solid-liquid mixed type aluminum electrolytic capacitor provided by the invention is used, the capacitor is more resistant to pressure, and the electrolyte does not leak from the sealing part under the conditions of high temperature and high humidity.
Description
Technical Field
The invention belongs to the field of electrolyte for capacitors, and particularly relates to electrolyte for a solid-liquid mixed electrolytic capacitor and the electrolytic capacitor.
Background
In AV equipment and automotive electrical equipment, there is an increasing demand for equipment reliability. The solid electrolytic capacitor is more excellent in low ESR (Equivalent Series Resistance) than the liquid electrolytic capacitor. However, the lack of a substance capable of repairing the defects of the dielectric oxide film in the solid electrolytic capacitor leads to an increase in leakage current and may even cause short-circuiting. Thus, a hybrid electrolytic capacitor has been proposed which uses an electrolyte solution for repairing an oxide film, while using a solid electrolyte such as a conductive polymer as an electrolyte material.
The conventional electrolyte for a hybrid electrolytic capacitor is generally suitable for a capacitor of 100W.V. and below. From the viewpoint of the operating voltage range, the conventional hybrid electrolytic capacitor can be used for a smoothing circuit or a control circuit on the power supply output side. The electrolyte for the hybrid electrolytic capacitor contains gamma-butyrolactone, ethylene glycol, etc. as the main solvent, and amidine phthalate, tetramethylammonium phthalate, ammonium adipate, triethylamine phthalate, etc. as the solute.
The existing mixed type aluminum electrolytic capacitor is not pressure-resistant, and the problem of leakage at the sealing rubber position of the capacitor can occur under the condition of high temperature and high humidity of the used electrolyte.
Disclosure of Invention
The invention aims to solve the technical problem that in the prior art, a mixed type aluminum electrolytic capacitor is not pressure-resistant, and leakage occurs at a sealing rubber part of the capacitor under the conditions of high temperature and high humidity, and provides an electrolyte for a solid-liquid mixed type electrolytic capacitor and the electrolytic capacitor.
The technical scheme adopted by the invention for solving the problems is as follows:
the invention provides an electrolyte for a solid-liquid mixed electrolytic capacitor, which comprises the following components:
a solvent, a primary solute, and compound a;
the solvent comprises an aprotic solvent;
the primary solute comprises an imidazolinium cation and an organic carboxylic anion;
the compound A is selected from compounds shown in a structural formula I:
wherein R is 1 ～R 6 Each independently selected from hydrogen atoms or alkyl groups with 1-5 carbon atoms, and the two groups are connected to form a ring or not.
Alternatively, compound A comprises one or more of N-methyl-N- [ 2-propyl ] acetamide, N-methyl-N- [ 2-butyl ] acetamide, and N-methyl-N- [2- (3-methylbutyl) ] acetamide.
Optionally, the content of the solvent is 60% to 96%, the content of the main solute is 3% to 39%, and the content of the compound a is 0.001% to 3%, based on 100% of the total weight of the electrolyte.
Optionally, the aprotic solvent includes one or both of a lactone-based compound and a sulfone compound.
Optionally, the lactone-based compound comprises one or more of gamma-butyrolactone, alpha-acetyl-gamma-butyrolactone, beta-butyrolactone, gamma-valerolactone, and delta-valerolactone;
the sulfone compound includes one or both of sulfolane and dimethylsulfone.
Optionally, the imidazolinium cation includes one or more of 1,2,3,4-tetramethylimidazolinium cation, 1,3,4-trimethyl-2-ethylimidazolinium cation, 1-ethyl-2,3-dimethylimidazolinium cation, 1,3-dimethyl-2,4-diethylimidazolinium cation, 1,2-dimethyl-3,4-diethylimidazolinium cation, 1-methyl-2,3,4-triethylimidazolinium cation, 1,2,3,4-tetraethylimidazolinium cation, 1,2,3-trimethylimidazolinium cation, 1,3-dimethyl-2-ethylimidazolinium cation, 1-ethyl-2,3-dimethylimidazolinium cation, and 1,2,3-triethylimidazolinium cation.
Optionally, the organic carboxylic acid anion comprises one or more of a saturated dicarboxylic acid anion having 6 to 20 carbon atoms, an unsaturated dicarboxylic acid anion having 4 to 8 carbon atoms, and a benzoic acid anion containing only one carboxyl group.
Optionally, the saturated dicarboxylic acid anion comprises one or more of adipic acid anion, pimelic acid anion, suberic acid anion, azelaic acid anion, sebacic acid anion, dodecanedioic acid anion, 2-ethyl-dodecanedioic acid anion, 2-butyl-suberic acid anion, and 4-ethyl-tetradecanedioic acid anion;
the unsaturated dicarboxylic acid anion comprises one or more of maleic acid anion, phthalic acid anion, terephthalic acid anion and isophthalic acid anion;
the benzoate anion containing only one carboxyl group is the 2-methyl-benzoate anion.
Optionally, the solvent further comprises a protic solvent;
the content of the protic solvent is 0-15% by taking the total weight of the electrolyte as 100%.
Optionally, the protic solvent comprises an alcoholic solvent selected from compounds represented by structural formula ii:
HO-(CH 2 CH 2 O) n -R m -OH
structural formula II
Wherein n is an integer of 0 to 200, m is an integer of 0 to 100, and n and m cannot be 0 at the same time;
r is alkyl with 2-3 carbon atoms or alkyl hydroxyl with 2-3 carbon atoms.
The invention also provides an aluminum electrolytic capacitor, which comprises a capacitor element consisting of an anode, a cathode and a diaphragm, a solid electrolyte and the electrolyte.
The invention provides an electrolyte for a solid-liquid mixed type electrolytic capacitor, which is added with an aprotic solvent, takes imidazolinium cations and organic carboxylic anions as main solutes and a compound A, wherein the compound A has the structure that:
R 1 ～R 6 each independently selected from a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and connected two by two to form a ring or a non-ring, the solvent containing an imidazolinium cation and an organic carboxylic acid anion is used in combination with the compound A, whereby the capacitor is more resistant to voltage, and the capacitor does not leak electrolyte from the sealing portion even under high temperature and high humidity conditions.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides an electrolyte for a solid-liquid mixed electrolytic capacitor, which comprises the following components:
a solvent, a primary solute, and compound a;
the solvent comprises an aprotic solvent;
the primary solute comprises an imidazolinium cation and an organic carboxylic anion;
the compound A is selected from compounds shown in a structural formula I:
wherein R is 1 ～R 6 Each independently selected from hydrogen atoms or alkyl groups with 1 to 5 carbon atoms, and the two groups are connected into a ring or not.
The invention provides an electrolyte for a solid-liquid mixed type electrolytic capacitor, which is added with an aprotic solvent, takes imidazolinium cations and organic carboxylic anions as main solutes and a compound A, wherein the compound A has the structure that:
R 1 ～R 6 each independently selected from a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and connected in pairs to form a ring or a non-ring, the solvent containing an imidazolinium cation and an organic carboxylic acid anion is used in combination with the compound A, whereby the capacitor is more resistant to pressure, and the electrolyte does not leak from the self-sealing portion of the capacitor even at high temperatures and high humidities.
In some more preferred embodiments, compound A may comprise one or more of N-methyl-N- [ 2-propyl ] acetamide, N-methyl-N- [ 2-butyl ] acetamide, and N-methyl-N- [2- (3-methylbutyl) ] acetamide.
In the present invention, imidazolinium cations and organic carboxylic anions are used as main solutes, and thus, the present invention is excellent in repairing defects of an oxide film, capable of reducing a leakage current, and excellent in thermal stability, and a capacitor using an electrolyte solution of the solute is more resistant to a voltage even at a high temperature and a high humidity.
In some embodiments of the present invention, the solvent is 60% to 96%, the primary solute is 3% to 39%, and the compound a is 0.001% to 3%, based on 100% of the total weight of the electrolyte.
In some embodiments of the invention, the aprotic solvent comprises one or both of a lactone-based compound and a sulfone compound.
In some embodiments of the invention, the lactone-type compound comprises one or more of gamma-butyrolactone, alpha-acetyl-gamma-butyrolactone, beta-butyrolactone, gamma-valerolactone, and delta-valerolactone;
the sulfone compound includes one or both of sulfolane and dimethylsulfone.
More preferably, the aprotic solvent may be selected from a mixed solvent formulated between γ -butyrolactone and sulfolane.
Addition of the sulfone compound contributes to replenishment of an oxide film in a defective portion of the dielectric layer, and can reduce leakage current of the electrolytic capacitor.
The selection of the solvent of the present invention can suppress the reduction of the electrolytic solution and the oxidation degradation of the solid electrolyte layer caused by the evaporation of the solvent to the outside of the electrolytic capacitor through the sealing member. Even when the electrolytic capacitor is exposed to a high-temperature environment for a long period of time, oxidation deterioration of the solid electrolyte layer is suppressed, the heat resistance of the electrolytic capacitor is improved, and the sealing body is inhibited from being corroded to cause leakage.
In some embodiments of the invention, the imidazolinium cation comprises one or more of 1,2,3,4-tetramethylimidazolinium cation, 1,3,4-trimethyl-2-ethylimidazolinium cation, 1-ethyl-2,3-dimethylimidazolinium cation, 1,3-dimethyl-2,4-diethylimidazolinium cation, 1,2-dimethyl-3,4-diethylimidazolinium cation, 1-methyl-2,3,4-triethylimidazolinium cation, 1,2,3,4-tetraethylimidazolinium cation, 1,2,3-trimethylimidazolinium cation, 1,3-dimethyl-2-ethylimidazolinium cation, 1-ethyl-2,3-dimethylimidazolinium cation, and 1,2,3-triethylimidazolinium cation.
More preferably, the imidazolinium comprises one or more of 1,2,3,4-tetramethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium.
In some embodiments of the invention, the organic carboxylic acid anion comprises one or more of a saturated dicarboxylic anion having 6 to 20 carbon atoms, an unsaturated dicarboxylic anion having 4 to 8 carbon atoms, and a benzoic anion containing only one carboxyl group.
In some embodiments of the invention, the saturated dicarboxylic acid anion comprises one or more of adipic acid anion, pimelic acid anion, suberic acid anion, azelaic acid anion, sebacic acid anion, dodecanedioic acid anion, 2-ethyl-dodecanedioic acid anion, 2-butyl-suberic acid anion, and 4-ethyl-tetradecabioic acid anion;
the unsaturated dicarboxylic acid anion comprises one or more of maleic acid anion, phthalic acid anion, terephthalic acid anion and isophthalic acid anion;
the benzoate anion containing only one carboxyl group is the 2-methyl-benzoate anion.
More preferably, the organic carboxylic acid anion comprises one or both of 2-ethyl-dodecanedioic acid, 2-butyl-suberic acid.
Aprotic solvents, due to their minimal or no tendency to undergo self-delivery reactions, are often used in admixture with protic solvents, typically to solubilize and disperse as well as dilute the primary solute.
In some embodiments of the invention, the solvent further comprises a protic solvent;
the content of the protic solvent is 0-15% by taking the total weight of the electrolyte as 100%.
The selection of the alcoholic solvent as the protic solvent reduces the ESR of the electrolytic capacitor and improves the heat resistance of the capacitor.
In some embodiments of the invention, the protic solvent comprises an alcoholic solvent selected from the group consisting of compounds of formula ii:
HO-(CH 2 CH 2 O) n -R m -OH
structural formula II
Wherein n is an integer of 0 to 200, m is an integer of 0 to 100, and n and m cannot be 0 at the same time;
r is alkyl with 2-3 carbon atoms or alkyl hydroxyl with 2-3 carbon atoms.
More preferably, when the protic solvent is selected from alcoholic solvents, one or more of ethylene glycol, propylene glycol, and diethylene glycol may be selected.
The invention also provides an aluminum electrolytic capacitor, which comprises a capacitor element consisting of an anode, a cathode and a diaphragm, a solid electrolyte and the electrolyte as described in any one of the above.
Wherein a capacitor element formed by winding an anode electrode foil and a cathode electrode foil with a separator interposed therebetween, a solid electrolyte layer formed by impregnating a conductive polymer dispersion, and a void portion in the capacitor element of the solid electrolyte layer are impregnated with the electrolyte solution described above.
In some embodiments of the present invention, the conductive polymer dispersion is formed by dispersing a conductive polymer in a solvent, and the conductive polymer is selected from one or more of polythiophene, polyaniline and polypyrrole conductive polymers.
More preferably, the conductive polymer dispersion may include, but is not limited to, the Poly (3,4-ethylenedioxythiophene) in the form of PEDOT (Poly (2,3-dihydrothieno-1,4-dioxin), poly (3,4-ethylenedioxythiophene))/PSS (Poly (sodium-p-styrenesulfonate), sodium polystyrene sulfonate) complex.
The electrolyte provided by the invention is used, and the withstand voltage of the solid-liquid mixed electrolytic capacitor can reach more than 160V.
The present invention will be further illustrated by the following examples. It is to be understood that the present invention is not limited to the following embodiments, and methods are regarded as conventional methods unless otherwise specified. Materials are commercially available from the open literature unless otherwise specified.
Example 1
This example is for explaining the electrolyte for solid-liquid hybrid electrolytic capacitor and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) 89.99 percent of gamma-butyrolactone
(2) Ethylene glycol 4%
(3) 2-butyl-suberic acid anion 3%
(4) 1-Ethyl-3-methylimidazolinium cation 3%
(5) N-methyl-N- [ 2-propyl ] acetamide 0.01%
The preparation method comprises the following steps:
(1) According to the components, 2-butyl-suberic acid anions and 1-ethyl-3-methylimidazolinium cations are mixed to prepare a main solute;
(2) According to the components, gamma-butyrolactone, main solute, ethylene glycol and N-methyl-N- [ 2-propyl ] acetamide are uniformly mixed to prepare the electrolyte, which is marked as S1.
Example 2
This example is for explaining the electrolyte for solid-liquid hybrid electrolytic capacitor and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) Gamma-butyrolactone 85.99%
(2) Ethylene glycol 4%
(3) Sebacic acid anion 5%
(4) 1-Ethyl-3-methylimidazolinium cation 5%
(5) N-methyl-N- [ 2-propyl ] acetamide 0.01%
The preparation method comprises the following steps:
(1) According to the components, firstly, mixing sebacic acid anions and 1-ethyl-3-methylimidazolium cations to prepare a main solute;
(2) According to the components, gamma-butyrolactone, main solute, ethylene glycol and N-methyl-N- [ 2-propyl ] acetamide are uniformly mixed to prepare the electrolyte, marked as S2.
Example 3
This example is for explaining the electrolyte solution for solid-liquid hybrid electrolytic capacitors and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) 91.9 percent of gamma-butyrolactone
(2) Ethylene glycol 4%
(3) 4-Ethyl-tetradecanedioic acid anion 2%
(4) 1,2,3,4-tetramethylimidazolinium cation 2%
(5) N-methyl-N- [ 2-propyl ] acetamide 0.1%
The preparation method comprises the following steps:
(1) According to the components, 4-ethyl-tetradecanedioic acid anion and 1,2,3,4-tetramethyl imidazolinium cation are mixed to prepare a main solute;
(2) According to the components, gamma-butyrolactone, main solute, ethylene glycol and N-methyl-N- [ 2-propyl ] acetamide are uniformly mixed to prepare electrolyte, which is marked as S3.
Example 4
This example is for explaining the electrolyte for solid-liquid hybrid electrolytic capacitor and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) Gamma-butyrolactone 77%
(2) Ethylene glycol 4%
(3) 2-methyl-benzoic acid anion 9%
(4) 1-Ethyl-3-methylimidazolinium cation 9%
(5) N-methyl-N- [ 2-propyl ] acetamide 1%
The preparation method comprises the following steps:
(1) According to the components, 2-methyl-benzoic acid anions and 1-ethyl-3-methylimidazolium cations are mixed to prepare a main solute;
(2) According to the components, gamma-butyrolactone, main solute, ethylene glycol and N-methyl-N- [ 2-propyl ] acetamide are uniformly mixed to prepare electrolyte, which is marked as S4.
Example 5
This example is for explaining the electrolyte solution for solid-liquid hybrid electrolytic capacitors and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) Gamma-butyrolactone 84.99%
(2) Ethylene glycol 5%
(3) 2-Ethyl-dodecanedioic acid anion 5%
(4) 1,2,3,4-Tetramethylimidazolinium cation 5%
(5) N-methyl-N- [ 2-propyl ] acetamide 0.01%
The preparation method comprises the following steps:
(1) According to the components, 2-ethyl-dodecanedioic acid anion and 1,2,3,4-tetramethyl imidazolinium cation are mixed to prepare a main solute;
(2) According to the components, gamma-butyrolactone, main solute, ethylene glycol and N-methyl-N- [ 2-propyl ] acetamide are uniformly mixed to prepare electrolyte, marked as S5.
Example 6
This example is for explaining the electrolyte for solid-liquid hybrid electrolytic capacitor and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) 89.5 percent of gamma-butyrolactone
(2) Ethylene glycol 4%
(3) 2-butyl-suberic acid anion 3%
(4) 1-Ethyl-3-methylimidazolinium cation 3%
(5) N-methyl-N- [ 2-butyl ] acetamide 0.5%
The preparation method comprises the following steps:
(1) According to the components, 2-butyl-suberic acid anions and 1-ethyl-3-methylimidazolinium cations are mixed to prepare a main solute;
(2) According to the above-mentioned components, gamma-butyrolactone, main solute, ethylene glycol and N-methyl-N- [ 2-butyl ] acetamide are uniformly mixed, and the electrolyte solution, marked as S6, is prepared.
Example 7
This example is for explaining the electrolyte solution for solid-liquid hybrid electrolytic capacitors and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) 89.97 percent of gamma-butyrolactone
(2) Ethylene glycol 4%
(3) 2-butyl-suberic acid anion 3%
(4) 1-Ethyl-3-methylimidazolinium cation 3%
(5) N-methyl-N- [2- (3-methylbutyl) ] acetamide 0.03%
The preparation method comprises the following steps:
(1) Mixing 2-butyl-suberic acid anions and 1-ethyl-3-methylimidazolinium cations to prepare a main solute according to the components;
(2) According to the components, gamma-butyrolactone, main solute, ethylene glycol and N-methyl-N- [2- (3-methylbutyl) ] acetamide are uniformly mixed to prepare electrolyte, and the electrolyte is marked as S7.
Comparative example 1
This example is for comparative illustration of the electrolyte for solid-liquid hybrid electrolytic capacitor and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) 89.99 percent of gamma-butyrolactone
(2) Ethylene glycol 4%
(3) 2-Ethyl-pentanoic acid anion 3%
(4) Ammonium ion 3%
(5) N-methyl-N- [ 2-propyl ] acetamide 0.01%
The preparation method comprises the following steps:
(1) According to the components, firstly, 2-ethyl-glutaric acid anions and ammonium ions are mixed to prepare a main solute;
(2) According to the above components, gamma-butyrolactone, main solute, ethylene glycol and N-methyl-N- [ 2-propyl ] acetamide are mixed uniformly to prepare a comparative electrolyte, marked as D1.
Comparative example 2
This example is for comparative illustration of the electrolyte for solid-liquid hybrid electrolytic capacitor and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) Ethylene glycol 93%
(2) 2-butyl-suberic acid anion 3%
(3) 1-Ethyl-3-methylimidazolinium cation 3%
(4) N-methyl-N- [ 2-propyl ] acetamide 1%
The preparation method comprises the following steps:
(1) According to the components, firstly, 2-ethyl-glutaric acid anions and ammonium ions are mixed to prepare a main solute;
(2) The main solute, ethylene glycol and N-methyl-N- [ 2-propyl ] acetamide were mixed uniformly according to the above components to prepare a comparative electrolyte, labeled D2.
Comparative example 3
This example is for comparative illustration of the electrolyte for solid-liquid hybrid electrolytic capacitor and the method for preparing the same disclosed in the present invention.
The electrolyte for preparing the solid-liquid mixed electrolytic capacitor comprises the following components by taking the total weight of the electrolyte as 100 percent:
(1) 90 percent of gamma-butyrolactone
(2) Ethylene glycol 4%
(3) 2-butyl-suberic acid anion 3%
(4) 1-Ethyl-3-methylimidazolinium cation 3%
The preparation method comprises the following steps:
(1) According to the components, 2-butyl-suberic acid anions and 1-ethyl-3-methylimidazolinium cations are mixed to prepare a main solute;
(2) According to the components, gamma-butyrolactone, main solute and ethylene glycol are uniformly mixed to prepare a comparative electrolyte, which is marked as D3.
Performance test
The performance tests were performed on S1 to S7 and comparative samples D1 to D3 obtained by the above preparation.
1. The prepared S1 to S7 and the comparative samples D1 to D3 are respectively subjected to conductivity, sparking voltage, liquid leakage and voltage resistance test of the capacitor.
(1) Electrical conductivity of
The conductivity of the electrolyte was measured using a thunder-magnetic DDSJ-308A conductivity meter at a temperature of 30 ℃.
(2) Sparking voltage
An intelligent test system for the TV-1000B aluminum foil characteristics of Nanjing Dagong electrons is adopted, 1cm x 0.5cm of unreacted Cheng Guangbo is adopted, the current is 20mA, and the sparking voltage of the electrolyte is tested at normal temperature.
(3) Liquid leakage
A capacitor element in which an anode aluminum foil and a cathode aluminum foil are wound with a separator interposed therebetween, and a solid electrolyte layer is formed by impregnating the capacitor element with a PEDOT/PSS water dispersion;
impregnating gaps in the capacitor element including the solid electrolyte layer with the electrolytes S1 to S7 and D1 to D3, respectively, to form a solid aluminum electrolytic hybrid capacitor (rated voltage 400V —, electrostatic capacity 10 μ f,10mm × l2 mm);
rated voltage is applied to the manufactured aluminum electrolytic capacitor, high-temperature and high-humidity tests (the temperature is 150 ℃, the relative humidity is 85 percent, and the aluminum electrolytic capacitor is placed for 72H) are carried out in a constant-temperature and constant-humidity box, the capacitor is taken out after the tests are finished, the state of sealing rubber is observed, wherein the sealing rubber is butyl rubber vulcanized by peroxide, and the number of the tests of the capacitor is 10pcs.
(4) Capacitor withstand voltage
A capacitor element in which an anode aluminum foil and a cathode aluminum foil are wound with a separator interposed therebetween, and a solid electrolyte layer is formed by impregnating the capacitor element with a PEDOT/PSS water dispersion;
a solid-state aluminum electrolytic hybrid capacitor (rated voltage 400V-, electrostatic capacity 10 μ f,10 mm. About. L20mm) was formed by impregnating the void portion in the capacitor element including the solid electrolyte layer with the electrolyte solution of the present invention;
the capacitor is charged, the power voltage is set to be 600V, the current is 20mA, and when the voltage rises to the value that cannot be continuously raised, the lower voltage value is recorded, and the value is the withstand voltage value of the capacitor.
The test results obtained are shown in table 1.
TABLE 1
As is clear from table 1, in examples S1 to S7 and comparative example D1, the main solutes used in examples S1 to S7 were formulated with an imidazolinium cation and an organic carboxylic acid anion, and the synergistic effect of compound a and the main solute prevented the capacitor from leaking the electrolyte from the seal portion, and in the expression of the voltage resistance of the capacitor, examples S1 to S7 were also superior.
It is understood from examples S1 to S7 and comparative example D2 that comparative example D2 uses only ethylene glycol as a main solvent, and examples S1 to S7 use an aprotic solvent to suppress leakage due to corrosion of the sealing body, and that the withstand voltage of examples S1 to S7 is also superior to that of comparative example D2 in the performance of the withstand voltage performance of the capacitor.
As is clear from examples S1 to S7 and comparative example D3, in comparative example D3, the compound a and the main solute were not combined with each other, and the leakage of the sealing body was serious, whereas the electrolytic solution did not leak from the sealing portion in the capacitors of examples S1 to S7.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The electrolyte for the solid-liquid mixed electrolytic capacitor is characterized by comprising the following components:
a solvent, a primary solute, and compound a;
the solvent comprises an aprotic solvent;
the primary solute comprises an imidazolinium cation and an organic carboxylic anion;
the compound A is selected from compounds shown in a structural formula I:
wherein R is 1 ～R 6 Each independently selected from hydrogen atoms or alkyl with 1-5 carbon atoms, and the two are connected to form a ring or not;
the content of the compound A is 0.001-3% by taking the total weight of the electrolyte as 100%.
2. The electrolyte of claim 1, wherein the compound a comprises one or more of N-methyl-N- [ 2-propyl ] acetamide, N-methyl-N- [ 2-butyl ] acetamide, and N-methyl-N- [2- (3-methylbutyl) ] acetamide.
3. The electrolyte according to claim 1, wherein the solvent is contained in an amount of 60 to 96% and the primary solute is contained in an amount of 3 to 39%, based on 100% by weight of the total electrolyte.
4. The electrolyte of claim 1, wherein the aprotic solvent comprises one or both of a lactone-based compound and a sulfone compound.
5. The electrolyte of claim 4, wherein the lactone-based compound comprises one or more of gamma-butyrolactone, alpha-acetyl-gamma-butyrolactone, beta-butyrolactone, gamma-valerolactone, and delta-valerolactone;
the sulfone compound includes one or both of sulfolane and dimethylsulfone.
6. The electrolyte of claim 1, wherein the imidazolinium cations include one or more of 1,2,3,4-tetramethylimidazolinium cation, 1,3,4-trimethyl-2-ethylimidazolinium cation, 1,3-dimethyl-2,4-diethylimidazolinium cation, 1,2-dimethyl-3,4-diethylimidazolinium cation, 1-methyl-2,3,4-triethylimidazolinium cation, 1,2,3,4-tetraethylimidazolinium cation, 1,2,3-trimethylimidazolinium cation, 1,3-dimethyl-2-ethylimidazolinium cation, 1-ethyl-2,3-dimethylimidazolinium cation, and 1,2,3-triethylimidazolinium cation.
7. The electrolyte of claim 1, wherein the organic carboxylic acid anion comprises one or more of a saturated dicarboxylic acid anion having 6 to 20 carbon atoms, an unsaturated dicarboxylic acid anion having 4 to 8 carbon atoms, and a benzoic acid anion having only one carboxyl group;
the saturated dicarboxylic acid anion includes one or more of adipic acid anion, pimelic acid anion, suberic acid anion, azelaic acid anion, sebacic acid anion, dodecanedioic acid anion, 2-ethyl-dodecanedioic acid anion, 2-butyl-suberic acid anion, and 4-ethyl-tetradecanedioic acid anion;
the unsaturated dicarboxylic acid anion comprises one or more of maleic acid anion, phthalic acid anion, terephthalic acid anion and isophthalic acid anion;
the benzoate anion containing only one carboxyl group is the 2-methyl-benzoate anion.
8. The electrolyte of any one of claims 1-7, wherein the solvent further comprises a protic solvent;
the content of the protic solvent is 0-15% by taking the total weight of the electrolyte as 100%.
9. The electrolyte of claim 8, wherein the protic solvent comprises an alcoholic solvent selected from the group consisting of compounds of formula ii:
HO-(CH 2 CH 2 O) n -R m -OH
structural formula II
Wherein n is an integer of 0 to 200, m is an integer of 0 to 100, and n and m cannot be 0 at the same time;
r is alkyl with 2-3 carbon atoms or alkyl hydroxyl with 2-3 carbon atoms.
10. An aluminum electrolytic capacitor comprising a capacitor element comprising an anode, a cathode, and a separator, a solid electrolyte, and the electrolyte according to any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225495A (en) * | 1998-01-28 | 1999-08-11 | 松下电器产业株式会社 | Electrolytic capacitor and method for making same |
| CN1229259A (en) * | 1998-03-17 | 1999-09-22 | 松下电器产业株式会社 | Electrochemical device |
| CN1467764A (en) * | 2002-06-05 | 2004-01-14 | 松下电器产业株式会社 | Electrolyte for driving electrolytic capacitor and electrolytic capacitor using the same electrolyte |
| CN1711616A (en) * | 2002-11-08 | 2005-12-21 | 日本贵弥功株式会社 | Electrolytic capacitor |
| CN101292308A (en) * | 2005-10-17 | 2008-10-22 | 三洋化成工业株式会社 | Electrolysis solution and electrolytic capacitor using the same |
-
2020
- 2020-05-07 CN CN202010384426.7A patent/CN113628885B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225495A (en) * | 1998-01-28 | 1999-08-11 | 松下电器产业株式会社 | Electrolytic capacitor and method for making same |
| CN1229259A (en) * | 1998-03-17 | 1999-09-22 | 松下电器产业株式会社 | Electrochemical device |
| CN1467764A (en) * | 2002-06-05 | 2004-01-14 | 松下电器产业株式会社 | Electrolyte for driving electrolytic capacitor and electrolytic capacitor using the same electrolyte |
| CN1711616A (en) * | 2002-11-08 | 2005-12-21 | 日本贵弥功株式会社 | Electrolytic capacitor |
| CN101292308A (en) * | 2005-10-17 | 2008-10-22 | 三洋化成工业株式会社 | Electrolysis solution and electrolytic capacitor using the same |
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