CN116612997B - Composite electrolyte for electrolytic capacitor - Google Patents
Composite electrolyte for electrolytic capacitor Download PDFInfo
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- CN116612997B CN116612997B CN202310900311.2A CN202310900311A CN116612997B CN 116612997 B CN116612997 B CN 116612997B CN 202310900311 A CN202310900311 A CN 202310900311A CN 116612997 B CN116612997 B CN 116612997B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 43
- 239000003990 capacitor Substances 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 28
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- -1 carboxylic acid ammonium salt Chemical class 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 150000002334 glycols Chemical class 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 10
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- VJCJAQSLASCYAW-UHFFFAOYSA-N azane;dodecanoic acid Chemical compound [NH4+].CCCCCCCCCCCC([O-])=O VJCJAQSLASCYAW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 5
- CFBYEGUGFPZCNF-UHFFFAOYSA-N 2-nitroanisole Chemical compound COC1=CC=CC=C1[N+]([O-])=O CFBYEGUGFPZCNF-UHFFFAOYSA-N 0.000 claims description 4
- SATJMZAWJRWBRX-UHFFFAOYSA-N azane;decanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCCCCCC([O-])=O SATJMZAWJRWBRX-UHFFFAOYSA-N 0.000 claims description 4
- 229940067597 azelate Drugs 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- ARKIFHPFTHVKDT-UHFFFAOYSA-N 1-(3-nitrophenyl)ethanone Chemical compound CC(=O)C1=CC=CC([N+]([O-])=O)=C1 ARKIFHPFTHVKDT-UHFFFAOYSA-N 0.000 claims description 2
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 claims description 2
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims 1
- 239000005871 repellent Substances 0.000 claims 1
- 239000011888 foil Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 230000008439 repair process Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005189 alkyl hydroxy group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
The invention relates to the technical field of electrolytic capacitors, and discloses a composite electrolyte for electrolytic capacitors, which consists of 60-70 parts of main solvent, 10-20 parts of auxiliary solvent, 15-25 parts of main solute, 5-12 parts of auxiliary solute, 0.1-0.5 part of hydrogen eliminating agent and 0.2-0.4 part of hydration-preventing auxiliary agent, wherein the auxiliary solute is a polyethylene glycol derivative containing four equivalent carboxylic acid ammonium salt in the structure, and the auxiliary solute is taken as a bridge, so that the solubility of the main solute in a solvent system is greatly improved, the conductivity of the electrolyte is enhanced, the leakage current of the electrolytic capacitor is reduced, the pressure resistance of the electrolytic capacitor is enhanced, the service life is prolonged, symmetrical hydroxyl is contained in the auxiliary solute structure, the repair capability and the repair efficiency of oxide film defects on an anode foil can be effectively enhanced through combination with active defect sites of the anode foil through chemical adsorption and electrochemical adsorption, and the high sparking voltage is shown.
Description
Technical Field
The invention relates to the technical field of electrolytic capacitors, in particular to a composite electrolyte for an electrolytic capacitor.
Background
Aluminum electrolytic capacitors are one of the basic elements of electronic products, and in recent years, aluminum electrolytic capacitors have been widely used in the industries of notebook computers, aerospace, precision instruments, automotive electronics, and the like. With the rapid development of electronic information technology, the assembly degree and integration degree of the electronic complete machine are higher and higher, so that the comprehensive performance requirement of the aluminum electrolytic capacitor is higher and higher, and particularly in industries such as high-speed rail, large-screen high-definition display, military informatization and the like, the development of the aluminum electrolytic capacitor with high voltage resistance and long service life is needed. The working electrolyte is used as the true cathode of the aluminum electrolytic capacitor, plays a decisive role in the comprehensive performances of leakage current, loss factor, voltage-withstanding capability, service life and the like of the aluminum electrolytic capacitor, and generally, the working electrolyte of the aluminum electrolytic capacitor mainly comprises solvents, solutes, hydrogen eliminator, water-proof auxiliary agents and other additives, wherein the types of the solutes are more than ten, and mainly comprise various carboxylic acids, ammonium salts thereof, various borates and the like.
The invention patent with the application number of CN201710130031.2 discloses a high polymer and application thereof in an electrolyte of an aluminum electrolytic capacitor, sorbic acid, vinyl n-butyl ether and vinyl acetate are used as polymerization monomers, free radical polymerization reaction is carried out under the action of an initiator to prepare the high polymer, ammonium salt of the high polymer is used as a solute of the electrolyte, ethylene glycol is used as a main solvent, and additives such as auxiliary solvent and hydrogen eliminator are compounded to form the electrolyte for the aluminum electrolytic capacitor, and the electrolyte has good conductivity and sparking voltage performance and good temperature resistance, and can meet the use requirements of the ultrahigh voltage aluminum electrolytic capacitor with the voltage of 600V and above.
Disclosure of Invention
The invention aims to provide a composite electrolyte for an electrolytic capacitor, which can lead the prepared electrolyte to have good sparking voltage and conductivity performance by preparing polyethylene glycol derivatives containing four equivalent carboxylic acid ammonium salts in the structure as auxiliary solutes.
The aim of the invention can be achieved by the following technical scheme:
the composite electrolyte for the electrolytic capacitor comprises the following raw materials in parts by weight: 60-70 parts of main solvent, 10-20 parts of auxiliary solvent, 15-25 parts of main solute, 5-12 parts of auxiliary solute, 0.1-0.5 part of hydrogen eliminating agent and 0.2-0.4 part of hydration-preventing auxiliary agent;
the auxiliary solute is a polyethylene glycol derivative containing four equivalents of ammonium carboxylate salt in the structure.
Further, the main solvent is ethylene glycol.
Further, the auxiliary solvent is any one or a combination of more of propylene glycol, gamma-butyrolactone, diethylene glycol, n-butanol or 3-methoxypropionitrile.
Further, the main solute is any one of ammonium azelate hydrogen, ammonium dodecanoate or ammonium sebacate.
Further, the hydrogen eliminating agent is any one or a combination of more of resorcinol, p-nitrobenzoic acid, p-nitrobenzyl alcohol, o-nitroanisole or m-nitroacetophenone.
Further, the waterproof auxiliary agent is any one or more of phosphoric acid, hypophosphorous acid, ammonium phosphate or hypophosphorous acid and ammonium salts thereof.
Further, the preparation method of the auxiliary solute comprises the following steps:
step one: mixing polyethylene glycol diglycidyl ether with ethanol, stirring, adding iminodiacetic acid, stirring, introducing nitrogen, stirring at 60-65deg.C for 4-8 hr, distilling under reduced pressure to remove low boiling substances and unreacted substances, cooling, and discharging to obtain polyethylene glycol tetracarboxylic acid intermediate;
step two: adding polyethylene glycol tetracarboxylic acid intermediate into ethanol, stirring and mixing, introducing ammonia gas, monitoring the pH value of the reaction liquid in real time, removing ammonia gas when the pH value of the reaction liquid is maintained to be alkalescent within 5min, distilling under reduced pressure to remove solvent, and standing for 9-12h at the ambient temperature of 0-5 ℃ to obtain auxiliary solute.
Further, in the first step, the polyethylene glycol diglycidyl ether has a weight average molecular weight of 560.
Further, in the second step, the pH value of the weak base is 7.5-8.0.
In the technical scheme, the structural end part of the polyethylene glycol diglycidyl ether is an epoxy group, so that the epoxy group at the molecular chain end of the polyethylene glycol diglycidyl ether can be subjected to ring-opening reaction with imino groups in an iminodiacetic acid structure, the epoxy group at the molecular chain end of the polyethylene glycol diglycidyl ether can be converted into four-equivalent carboxyl functional groups, two-equivalent hydroxyl groups can be generated due to the ring-opening reaction, a polyethylene glycol tetracarboxylic acid intermediate is prepared, and carboxyl groups in the structure of the intermediate are aminated by ammonia gas to form ammonium salts, so that the polyethylene glycol derivative containing four-equivalent carboxylic acid ammonium salts in the structure, namely auxiliary solutes, is prepared.
Further, the preparation method of the composite electrolyte comprises the following steps:
the first step: stirring and mixing the main solvent and the auxiliary solvent in parts by weight, increasing the temperature to 120-130 ℃, uniformly stirring to form a mixed solvent, and continuously adding the main solute and the auxiliary solute in parts by weight when the mixed solvent is naturally cooled to 90-100 ℃, and carrying out heat preservation and stirring for 30-40min to form a mixed solution;
and a second step of: when the temperature of the mixed solution is naturally cooled to 80-90 ℃, adding the hydrogen eliminating agent and the hydration assistant in parts by weight into the mixed solution, and after heat preservation and stirring for 1-2h, naturally cooling to room temperature to obtain the composite electrolyte.
The invention has the beneficial effects that:
(1) The polyethylene glycol derivative containing four-equivalent carboxylic acid ammonium salt in the structure is prepared as an auxiliary solute, and because the molecular chain of the auxiliary solute contains a large number of polyether segments, hydrogen bonding effect can be generated between the auxiliary solute and polar parts such as a mixed solvent system, an anode foil oxide film and the like, so that the solubility of the auxiliary solute in a solvent is greatly improved, and meanwhile, a large number of alkyl groups in the polyethylene glycol structure can have good affinity with main solute molecules with long alkyl chains, so that the solubility of the main solute in the solvent system is greatly improved by taking the auxiliary solute as a bridge, the conductivity of electrolyte can be enhanced, the leakage current of an electrolytic capacitor is reduced, and the permeation of the solution to micropores and defects of the anode foil oxide film is facilitated, so that the pressure resistance of the electrolytic capacitor is effectively improved, and the electrolytic capacitor has longer service life.
(2) The auxiliary solute structure prepared by the invention contains symmetrical hydroxyl generated by ring opening reaction, and can be combined with active defect sites of anode foil through chemical adsorption and electrochemical adsorption, so that the repair capability and repair efficiency of oxide film defects on the anode foil are effectively enhanced.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a polyethylene glycol tetracarboxylic acid intermediate of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the process for preparing a cofactor comprises the steps of:
step one: mixing 2.4g of polyethylene glycol diglycidyl ether with weight average molecular weight of 560 with ethanol, stirring uniformly, adding 1.4g of iminodiacetic acid continuously, mixing uniformly, introducing nitrogen for protection, preserving heat and stirring for 6 hours at 60 ℃, then distilling under reduced pressure to remove low-boiling substances and unreacted substances, cooling and discharging to obtain a polyethylene glycol tetracarboxylic acid intermediate;
the structure of the polyethylene glycol tetracarboxylic acid intermediate was measured by potassium bromide tabletting using a Nicolet Magna IR550 type Fourier transform infrared spectrometerScanning with a scanning area of 4000-500 cm -1 The test results are shown in FIG. 1, and as can be seen from FIG. 1, 3391cm -1 Characteristic absorption peak of alkylhydroxy appears at 2850-2920 cm -1 The characteristic absorption peak of ethyl C-H in polyethylene glycol appears at 1728cm -1 Characteristic absorption peaks ascribed to C=O in the carboxylic acid group appear at 1202cm -1 Characteristic absorption peak of C-N appears at 1112cm -1 The structural end part of the polyethylene glycol diglycidyl ether contains epoxy groups, and can carry out ring-opening reaction with imino groups in an iminodiacetic acid structure, so that the epoxy groups at the molecular chain end of the polyethylene glycol diglycidyl ether are converted into four equivalent carboxyl functional groups, and hydroxyl groups can be generated in the ring-opening reaction process, so that the polyethylene glycol tetracarboxylic acid intermediate contains not only carboxyl functional groups but also active hydroxyl functional groups.
Step two: adding polyethylene glycol tetracarboxylic acid intermediate into ethanol, stirring and mixing, introducing ammonia gas, monitoring the pH value of the reaction liquid in real time, removing ammonia gas when the pH value of the reaction liquid is maintained at 7.5 within 5min, distilling under reduced pressure to remove solvent, placing in a refrigerator, setting the temperature in the refrigerator to be 0 ℃, standing for 12h, and taking out to obtain auxiliary solute.
Example 1
The composite electrolyte for the electrolytic capacitor comprises the following raw materials in parts by weight: 60 parts of main solvent ethylene glycol, 10 parts of auxiliary solvent propylene glycol, 15 parts of main solute ammonium azelate hydrogen, 5 parts of auxiliary solute, 0.1 part of hydrogen eliminator resorcinol and 0.2 part of hydration assistant phosphoric acid;
the preparation method of the composite electrolyte comprises the following steps:
the first step: stirring and mixing the main solvent glycol and the auxiliary solvent propylene glycol in parts by weight, increasing the temperature to 120 ℃, uniformly stirring to form a mixed solvent, and continuously adding the main solute ammonium azelate and the auxiliary solute in parts by weight when the mixed solvent is naturally cooled to 100 ℃, and carrying out heat preservation and stirring for 30min to form a mixed solution;
and a second step of: when the temperature of the mixed solution is naturally cooled to 80 ℃, adding resorcinol serving as a hydrogen eliminating agent and phosphoric acid serving as a hydration auxiliary agent in parts by weight into the mixed solution, and after heat preservation and stirring for 1h, naturally cooling to room temperature to obtain the composite electrolyte.
Example 2
The composite electrolyte for the electrolytic capacitor comprises the following raw materials in parts by weight: 65 parts of main solvent ethylene glycol, 18 parts of auxiliary solvent gamma-butyrolactone, 24 parts of main solute ammonium dodecanoate, 10 parts of auxiliary solute, 0.4 part of hydrogen eliminating agent p-nitrobenzoic acid and 0.3 part of hydration-preventing auxiliary agent hypophosphorous acid;
the preparation method of the composite electrolyte comprises the following steps:
the first step: stirring and mixing the main solvent glycol and the auxiliary solvent gamma-butyrolactone in parts by weight, increasing the temperature to 130 ℃, uniformly stirring to form a mixed solvent, and continuously adding the main solute ammonium dodecanoate and the auxiliary solute into the mixed solvent when the mixed solvent is naturally cooled to 100 ℃, and carrying out heat preservation and stirring for 40min to form a mixed solution;
and a second step of: when the temperature of the mixed solution is naturally cooled to 90 ℃, adding the p-nitrobenzoic acid serving as a hydrogen eliminating agent and hypophosphorous acid serving as a hydration auxiliary agent into the mixed solution, preserving heat and stirring for 2 hours, and naturally cooling to room temperature to obtain the composite electrolyte.
Example 3
The composite electrolyte for the electrolytic capacitor comprises the following raw materials in parts by weight: 70 parts of main solvent glycol, 20 parts of auxiliary solvent n-butanol, 25 parts of main solute ammonium sebacate, 12 parts of auxiliary solute, 0.5 part of hydrogen eliminator o-nitroanisole and 0.4 part of hydration-preventing auxiliary agent phosphoric acid;
the preparation method of the composite electrolyte comprises the following steps:
the first step: stirring and mixing the main solvent glycol and the auxiliary solvent n-butanol in parts by weight, increasing the temperature to 130 ℃, uniformly stirring to form a mixed solvent, and continuously adding the main solute ammonium sebacate and the auxiliary solute in parts by weight when the mixed solvent is naturally cooled to 100 ℃, and carrying out heat preservation and stirring for 40min to form a mixed solution;
and a second step of: when the temperature of the mixed solution is naturally cooled to 90 ℃, adding the hydrogen eliminating agent o-nitroanisole and the hydration assistant phosphoric acid in parts by weight into the mixed solution, preserving heat and stirring for 2 hours, and naturally cooling to room temperature to obtain the composite electrolyte.
Comparative example 1
The composite electrolyte for the electrolytic capacitor comprises the following raw materials in parts by weight: 65 parts of main solvent glycol, 18 parts of auxiliary solvent gamma-butyrolactone, 24 parts of main solute ammonium dodecanoate, 0.4 part of hydrogen eliminator p-nitrobenzoic acid and 0.3 part of hydration-preventing auxiliary agent hypophosphorous acid;
the preparation method of the composite electrolyte comprises the following steps:
the first step: stirring and mixing the main solvent glycol and the auxiliary solvent gamma-butyrolactone in parts by weight, increasing the temperature to 130 ℃, uniformly stirring to form a mixed solvent, and continuously adding the main solute ammonium dodecanoate in parts by weight when the mixed solvent is naturally cooled to 100 ℃, and carrying out heat preservation and stirring for 40min to form a mixed solution;
and a second step of: when the temperature of the mixed solution is naturally cooled to 85 ℃, adding the p-nitrobenzoic acid serving as a hydrogen eliminating agent and hypophosphorous acid serving as a hydration auxiliary agent into the mixed solution, preserving heat and stirring for 2 hours, and naturally cooling to room temperature to obtain the composite electrolyte.
Performance detection
The composite electrolytes prepared in examples 1 to 3 and comparative example 1 of the present invention were subjected to a sparking voltage at 30℃using a Yangzhou Bao European TV-1CH type intelligent TV tester; the composite electrolytes prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention were tested for conductivity at 30℃using a DDSJ-308F bench conductivity tester, and set to a current density of 40A/cm 2 The test results are recorded in table 1:
TABLE 1 test results of composite electrolyte Performance
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Sparking voltage/V | 619 | 625 | 624 | 437 |
| Conductivity/ms/cm | 1.84 | 1.87 | 1.85 | 1.12 |
From the data in table 1, it can be observed that the composite electrolytes prepared in examples 1 to 3 of the present invention have higher sparking voltage and conductivity, and thus have good repair ability of anode foil and lower leakage current. The composite electrolyte prepared in comparative example 1 has low sparking voltage and conductivity values, and it can be reasonably speculated that the non-addition of the auxiliary solute results in poor solubility of the main solute in the mixed solvent system, and the anode foil cannot be repaired in a chemical or electrochemical adsorption mode, so that the sparking voltage and the conductivity values are poor.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (7)
1. The composite electrolyte for the electrolytic capacitor is characterized by comprising the following raw materials in parts by weight: 60-70 parts of main solvent, 10-20 parts of auxiliary solvent, 15-25 parts of main solute, 5-12 parts of auxiliary solute, 0.1-0.5 part of hydrogen eliminating agent and 0.2-0.4 part of hydration-preventing auxiliary agent;
the auxiliary solute is a polyethylene glycol derivative containing tetracarboxylic acid ammonium salt in the structure;
the preparation method of the auxiliary solute comprises the following steps:
step one: mixing polyethylene glycol diglycidyl ether with ethanol, stirring, adding iminodiacetic acid, stirring, introducing nitrogen, stirring at 60-65deg.C for 4-8 hr, distilling under reduced pressure to remove low boiling substances and unreacted substances, cooling, and discharging to obtain polyethylene glycol tetracarboxylic acid intermediate;
step two: adding polyethylene glycol tetracarboxylic acid intermediate into ethanol, stirring and mixing, introducing ammonia gas, monitoring the pH value of the reaction liquid in real time, removing ammonia gas when the pH value of the reaction liquid is maintained to be alkalescent within 5min, distilling under reduced pressure to remove solvent, and standing for 9-12h at the ambient temperature of 0-5 ℃ to obtain auxiliary solute;
the weight average molecular weight of the polyethylene glycol diglycidyl ether is 560;
the pH value of the alkalescence is 7.5-8.0.
2. The composite electrolyte for electrolytic capacitors as recited in claim 1, wherein the main solvent is ethylene glycol.
3. The composite electrolyte for electrolytic capacitors according to claim 1, wherein the auxiliary solvent is any one or a combination of a plurality of propylene glycol, γ -butyrolactone, diethylene glycol, n-butanol or 3-methoxypropionitrile.
4. The composite electrolyte for electrolytic capacitors as recited in claim 1, wherein the main solute is any one of ammonium azelate, ammonium dodecanoate, or ammonium sebacate.
5. The composite electrolyte for electrolytic capacitors according to claim 1, wherein the hydrogen eliminator is any one or a combination of more of resorcinol, p-nitrobenzoic acid, p-nitrobenzyl alcohol, o-nitroanisole or m-nitroacetophenone.
6. The composite electrolyte for electrolytic capacitors according to claim 1, wherein the water-repellent auxiliary agent is any one or a combination of a plurality of phosphoric acid, hypophosphorous acid, ammonium phosphate salts or hypophosphorous acid and ammonium salts thereof.
7. The composite electrolyte for electrolytic capacitors according to claim 1, wherein the preparation method of the composite electrolyte comprises the steps of:
the first step: stirring and mixing the main solvent and the auxiliary solvent, increasing the temperature to 120-130 ℃, uniformly stirring to form a mixed solvent, continuously adding the main solute and the auxiliary solute into the mixed solvent when the mixed solvent is naturally cooled to 90-100 ℃, and carrying out heat preservation and stirring for 30-40min to form a mixed solution;
and a second step of: when the temperature of the mixed solution is naturally cooled to 80-90 ℃, adding a hydrogen eliminating agent and a hydration-preventing auxiliary agent into the mixed solution, preserving heat and stirring for 1-2h, and naturally cooling to room temperature to obtain the composite electrolyte.
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