CN116525304B - Preparation method of solid-liquid mixed electrolytic capacitor - Google Patents
Preparation method of solid-liquid mixed electrolytic capacitor Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 60
- 239000003990 capacitor Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 239000011888 foil Substances 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000006184 cosolvent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 238000004804 winding Methods 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 36
- 229920000128 polypyrrole Polymers 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 9
- 229960004889 salicylic acid Drugs 0.000 claims description 9
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 229920005549 butyl rubber Polymers 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 238000003466 welding Methods 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 238000000593 microemulsion method Methods 0.000 claims description 2
- -1 p-nitromethanol Chemical compound 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/02—Machines for winding capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/04—Drying; Impregnating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/08—Housing; Encapsulation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/151—Solid electrolytic capacitors with wound foil electrodes
-
- 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
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Abstract
The invention relates to the technical field of electrolytic capacitors, and discloses a preparation method of a solid-liquid mixed electrolytic capacitor, which comprises the steps of inserting an anode aluminum foil, a cathode carbon foil and an anode guide pin into electrolytic paper, winding to form a core package, carrying out formation treatment on the core package, immersing the core package into a solid-liquid mixed electrolytic solution for impregnation treatment, and finally carrying out packaging operation to obtain the solid-liquid mixed electrolytic capacitor, wherein the solid-liquid mixed electrolytic solution consists of a main solvent, a cosolvent, a conductive nano polymer and the like, the conductivity of the electrolytic solution can be greatly improved due to the existence of the conductive nano polymer, the conductive nano polymer has smaller particle size, more conductive nano polymer is loaded in the impregnation process of the core package, the capacitance of the solid-liquid mixed electrolytic capacitor is improved, and the capacity of the solid-liquid mixed electrolytic capacitor can be effectively improved due to the combination of other components in the electrolytic solution.
Description
Technical Field
The invention relates to the technical field of electrolytic capacitors, in particular to a preparation method of a solid-liquid mixed electrolytic capacitor.
Background
A capacitor is a basic electronic component that stores charge under an applied voltage by adding a layer of non-conductive dielectric material to two adjacent conductors. According to different manufacturing materials, capacitors can be classified into aluminum electrolytic capacitors, niobium electrolytic capacitors, film capacitors, mica capacitors, ceramic capacitors and the like, wherein the aluminum electrolytic capacitors have large capacitance per unit volume, small volume, light weight and low price, and are widely applied in daily life. Among aluminum electrolytic capacitors, conductive polymer solid aluminum electrolytic capacitors and liquid aluminum electrolytic capacitors are also classified, and in recent years, solid-liquid hybrid aluminum electrolytic capacitors have received a great deal of attention because they can combine the advantages of conductive polymer solid aluminum electrolytic capacitors and liquid aluminum electrolytic capacitors, and are gradually applied to industries such as new energy automobiles, high-power fast charging, industrial frequency converters, and the like.
As one of the core components of the aluminum electrolytic capacitor, the development of the electrolyte is gradually in progress, the electrolyte mainly comprises a solvent, a solute and an additive, wherein the solvent is used as the main body of the electrolyte and mainly plays a role in dispersing and dissolving the solute, the solute is used as the core part of the electrolyte and mainly plays a role in improving the conductivity of the electrolyte, and the additive plays a role in improving, and although the existing electrolyte can meet the requirements of relevant test parameters of the electrolyte, with the rapid development of the electronic industry and large industrial equipment, higher requirements are put forward on the comprehensive properties such as the conductivity, the capacity extraction rate and the like of the aluminum electrolytic capacitor.
Based on the above, the invention provides the solid-liquid mixed electrolyte which has higher conductivity, can be directly applied to the aluminum electrolytic capacitor, and achieves the purpose of improving the comprehensive performances of the aluminum electrolytic capacitor, such as capacitance, capacity extraction rate and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a solid-liquid mixed electrolytic capacitor, which solves the problem of poor electrochemical performance such as conductivity and the like of the traditional electrolytic capacitor.
The aim of the invention can be achieved by the following technical scheme:
a method for preparing a solid-liquid mixed electrolytic capacitor, comprising the steps of:
step one: inserting an anode aluminum foil and a cathode carbon foil with oxide films on the surfaces and anode guide pins into electrolytic paper, and winding to form a core package;
step two: drying the core bag, spot-welding the core bag on an iron bar, and performing formation charging;
step three: drying the core bag subjected to the formation operation, immersing the core bag into a solid-liquid mixed electrolyte, and carrying out impregnation treatment;
step four: drying the impregnated core package, loading the core package into an aluminum shell, packaging the core package by using butyl rubber, and aging the core package to obtain a solid-liquid mixed electrolytic capacitor;
the solid-liquid mixed electrolyte comprises the following raw materials in parts by weight: 50-60 parts of main solvent, 10-20 parts of cosolvent, 4-8 parts of conductive nano polymer, 2-4 parts of ammonium formate, 1-3 parts of p-nitromethanol, 0.5-1 part of salicylic acid, 0.5-2 parts of boric acid and 0.1-0.5 part of phosphoric acid;
the conductive nano polymer is prepared by preparing nano polypyrrole by a microemulsion method and then grafting thiophene groups.
Further, the main solvent is ethylene glycol; the cosolvent is any one of gamma-butyrolactone, sulfolane or dimethyl sulfoxide.
Further, the preparation method of the solid-liquid mixed electrolyte comprises the following preparation steps:
the first step: mixing a main solvent and a cosolvent in parts by weight to form a uniform solution, raising the temperature to 60-80 ℃, adding a conductive nano polymer in parts by weight, and performing ultrasonic dispersion for 20-40min to obtain an electrolytic premix;
and a second step of: adding ammonium formate, p-nitromethanol, salicylic acid, boric acid and phosphoric acid into the electrolytic premix solution, stirring and mixing for 5-10min at 80-90 ℃, standing for 10-15min, and naturally cooling to obtain the solid-liquid mixed electrolyte.
Further, the preparation method of the conductive nano polymer comprises the following preparation steps:
step S1: dissolving sodium dodecyl sulfate in pure water, stirring for 30-60min, adding pyrrole monomer, stirring at 100-200rpm for 1-2h, reducing the rotation speed to 20-40rpm, adding glycerol, and stirring to form uniform solution;
step S2: dissolving ammonium persulfate in pure water to prepare an initiator solution, dripping the initiator solution into the uniform solution prepared in the step S1, stirring the solution at room temperature for 12 to 24 hours after the addition, centrifugally separating a solid product, washing the solid product by using acetone and the pure water, and carrying out vacuum drying to obtain nano polypyrrole;
step S3: dispersing nano polypyrrole in 65-75% ethanol water solution by volume fraction, adding 2-bromothiophene and alkaline catalyst, mixing, raising the system temperature to 60-70 ℃, stirring for 12-24h, discharging, centrifugally separating solid materials, washing, and vacuum drying to obtain the conductive nano polymer.
According to the technical scheme, sodium dodecyl sulfate is used as an emulsifier, glycerol is used as an auxiliary emulsifier, and the nano polypyrrole is prepared by using a microemulsion polymerization mode, and because the polypyrrole structure contains abundant secondary amino groups, nucleophilic substitution reaction can be carried out on the nano polypyrrole structure and halogen groups in the 2-bromothiophene structure under alkaline conditions, a large number of thiophene groups are introduced into the nano polypyrrole structure, and the conductive nano polymer is obtained.
Further, in the step S1, the mass ratio of the sodium dodecyl sulfate to the pure water to the pyrrole monomer to the glycerin is 3-5:40-60:1:0.2-0.4.
Further, in the step S2, the mass percentage concentration of the initiator solution is 4-8%.
Further, in step S2, the volume ratio of the initiator solution to the homogeneous solution is 1:4-6.
Further, in step S3, the mass ratio of the nano polypyrrole to the 2-bromothiophene is 1:0.1-0.25.
Further, in step S3, the alkaline catalyst is sodium hydroxide or potassium hydroxide.
The invention has the beneficial effects that:
(1) According to the invention, the specific surface area of the nano polypyrrole can be increased, the order degree in the electrolyte solvent is increased, so that the conductivity of the electrolyte can be effectively enhanced, after the thiophene group is introduced into the nano polypyrrole structure, the chemical bond is utilized, the electron transmission energy barrier between the polypyrrole and the thiophene group can be reduced, the mobility of carriers is improved, the conductivity of the nano polypyrrole can be further enhanced, and the conductivity of the electrolyte is further improved.
(2) In the process of preparing the solid-liquid mixed electrolytic capacitor, the core is required to be immersed in the solid-liquid mixed electrolytic solution, and the conductive nano polymer component contained in the electrolytic solution is required to enter the pores of the aluminum foil in the core package, so that the conductive polymer is required to have smaller particle size.
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 electron microscope image of the nano polypyrrole in embodiment 1 of the present invention, wherein a is a scanning electron microscope image and B is a transmission electron microscope image.
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.
Example 1
1. Preparation of conductive nano-polymers
Step S1: dissolving 4g of sodium dodecyl sulfate in 50mL of pure water, stirring for 40min, adding 1g of pyrrole monomer, stirring for 1h at a rotation speed of 200rpm, reducing the rotation speed to 30rpm, adding 0.3g of glycerol, and stirring to form a uniform solution;
step S2: dissolving ammonium persulfate in pure water to prepare an initiator solution with the mass percent concentration of 5%, dripping 10mL of the initiator solution into 50mL of the uniform solution prepared in the step S1, stirring at room temperature for 18h after the addition, centrifugally separating a solid product, washing with acetone and pure water, and drying in vacuum to obtain nano polypyrrole;
the nano polypyrrole is analyzed by using a Quanta 250 FEG scanning electron microscope and an H800 transmission electron microscope respectively, the test results are shown in figure 1, wherein A is a scanning electron microscope image, and B is a transmission electron microscope image, and the nano polypyrrole has a spherical shape, a smaller particle size and an average particle size smaller than 30nm.
Step S3: dispersing 2g of nano polypyrrole in 70% ethanol water solution by volume fraction, adding 0.25g of 2-bromothiophene and 6g of potassium hydroxide, uniformly mixing, raising the system temperature to 60 ℃, stirring for 16 hours, discharging, centrifugally separating solid materials, washing, and drying in vacuum to obtain the conductive nano polymer.
Respectively taking 0.5g of nano polypyrrole and conductive nano polymer samples, performing element analysis on the samples by using a TQ-3C element analyzer, and testing that the carbon element content in the conductive nano polymer samples is 72.69%, the hydrogen element content is 7.10%, the sulfur element content is 1.85%, the carbon element content in the nano polypyrrole samples is 71.34%, the hydrogen element content is 7.85%, and the sulfur element is not contained, wherein the imino groups in the nano polypyrrole structure and halogen groups in the 2-bromothiophene structure are subjected to nucleophilic substitution reaction, and the thiophene groups are introduced while the dehydrogenation is carried out.
2. Preparation of solid-liquid mixed electrolyte
The first step: mixing 50 parts of main solvent glycol and 10 parts of cosolvent gamma-butyrolactone to form a uniform solution, increasing the temperature to 60 ℃, adding 4 parts of conductive nano polymer, and performing ultrasonic dispersion for 20min to obtain electrolytic premix;
and a second step of: 2 parts of ammonium formate, 1 part of p-nitromethanol, 0 part of salicylic acid, 0.5 part of boric acid and 0.1 part of phosphoric acid are added into the electrolytic premix solution, stirred and mixed for 5min at the temperature of 80 ℃, and after standing for 10min, the mixture is naturally cooled to obtain a solid-liquid mixed electrolyte.
3. Preparation of solid-liquid mixed electrolytic capacitor
Step one: inserting an anode aluminum foil and a cathode carbon foil with oxide films on the surfaces and anode guide pins into electrolytic paper, and winding to form a core package;
step two: drying the core bag, spot-welding the core bag on an iron bar, and performing formation charging;
step three: drying the core bag subjected to the formation operation, immersing the core bag into a solid-liquid mixed electrolyte, and carrying out impregnation treatment;
step four: and (3) drying the impregnated core package, loading the core package into an aluminum shell, packaging the core package by using butyl rubber, and aging the core package to obtain the solid-liquid mixed electrolytic capacitor.
Example 2
1. Preparation of solid-liquid mixed electrolyte
The first step: mixing 55 parts of main solvent ethylene glycol and 12 parts of cosolvent sulfolane to form a uniform solution, increasing the temperature to 70 ℃, adding 6 parts of conductive nano polymer, and performing ultrasonic dispersion for 30min to obtain an electrolytic premix;
and a second step of: 3 parts of ammonium formate, 2 parts of p-nitromethanol, 0.6 part of salicylic acid, 0.8 part of boric acid and 0.3 part of phosphoric acid are added into the electrolytic premix solution, stirred and mixed for 6min at the temperature of 85 ℃, and after standing for 12min, the solution is naturally cooled to obtain a solid-liquid mixed electrolyte.
Wherein the conductive nano-polymer was prepared in the same manner as in example 1.
2. Preparation of solid-liquid mixed electrolytic capacitor
Step one: inserting an anode aluminum foil and a cathode carbon foil with oxide films on the surfaces and anode guide pins into electrolytic paper, and winding to form a core package;
step two: drying the core bag, spot-welding the core bag on an iron bar, and performing formation charging;
step three: drying the core bag subjected to the formation operation, immersing the core bag into a solid-liquid mixed electrolyte, and carrying out impregnation treatment;
step four: and (3) drying the impregnated core package, loading the core package into an aluminum shell, packaging the core package by using butyl rubber, and aging the core package to obtain the solid-liquid mixed electrolytic capacitor.
Example 3
1. Preparation of solid-liquid mixed electrolyte
The first step: mixing 60 parts of main solvent glycol and 20 parts of cosolvent dimethyl sulfoxide to form a uniform solution, increasing the temperature to 80 ℃, adding 8 parts of conductive nano polymer, and performing ultrasonic dispersion for 40min to obtain electrolytic premix;
and a second step of: 4 parts of ammonium formate, 3 parts of p-nitromethanol, 1 part of salicylic acid, 2 parts of boric acid and 0.5 part of phosphoric acid are added into the electrolytic premix solution, stirred and mixed for 10min at the temperature of 90 ℃, and after standing for 15min, the mixture is naturally cooled to obtain a solid-liquid mixed electrolyte.
Wherein the conductive nano-polymer was prepared in the same manner as in example 1.
2. Preparation of solid-liquid mixed electrolytic capacitor
Step one: inserting an anode aluminum foil and a cathode carbon foil with oxide films on the surfaces and anode guide pins into electrolytic paper, and winding to form a core package;
step two: drying the core bag, spot-welding the core bag on an iron bar, and performing formation charging;
step three: drying the core bag subjected to the formation operation, immersing the core bag into a solid-liquid mixed electrolyte, and carrying out impregnation treatment;
step four: and (3) drying the impregnated core package, loading the core package into an aluminum shell, packaging the core package by using butyl rubber, and aging the core package to obtain the solid-liquid mixed electrolytic capacitor.
Comparative example 1
1. Preparation of solid-liquid mixed electrolyte
The first step: mixing 55 parts of main solvent ethylene glycol and 12 parts of cosolvent sulfolane to form a uniform solution, increasing the temperature to 70 ℃, adding 6 parts of nano polypyrrole, and performing ultrasonic dispersion for 30min to obtain an electrolytic premix;
and a second step of: 3 parts of ammonium formate, 2 parts of p-nitromethanol, 0.6 part of salicylic acid, 0.8 part of boric acid and 0.3 part of phosphoric acid are added into the electrolytic premix solution, stirred and mixed for 6min at the temperature of 85 ℃, and after standing for 12min, the solution is naturally cooled to obtain a solid-liquid mixed electrolyte.
Wherein the preparation method of the nano polypyrrole is the same as that of the example 1.
2. Preparation of solid-liquid mixed electrolytic capacitor
Step one: inserting an anode aluminum foil and a cathode carbon foil with oxide films on the surfaces and anode guide pins into electrolytic paper, and winding to form a core package;
step two: drying the core bag, spot-welding the core bag on an iron bar, and performing formation charging;
step three: drying the core bag subjected to the formation operation, immersing the core bag into a solid-liquid mixed electrolyte, and carrying out impregnation treatment;
step four: and (3) drying the impregnated core package, loading the core package into an aluminum shell, packaging the core package by using butyl rubber, and aging the core package to obtain the solid-liquid mixed electrolytic capacitor.
Comparative example 2
1. Preparation of electrolyte
Mixing 55 parts of main solvent ethylene glycol and 12 parts of cosolvent sulfolane to form a uniform solution, raising the temperature to 70 ℃, adding 3 parts of ammonium formate, 2 parts of p-nitromethanol, 0.6 part of salicylic acid, 0.8 part of boric acid and 0.3 part of phosphoric acid, stirring and mixing for 6min in a temperature environment of 85 ℃, standing for 12min, and naturally cooling to obtain the electrolyte.
2. Preparation of electrolytic capacitor
Step one: inserting an anode aluminum foil and a cathode carbon foil with oxide films on the surfaces and anode guide pins into electrolytic paper, and winding to form a core package;
step two: drying the core bag, spot-welding the core bag on an iron bar, and performing formation charging;
step three: drying the core bag subjected to the formation operation, immersing the core bag into electrolyte, and carrying out impregnation treatment;
step four: and (3) drying the impregnated core package, loading the core package into an aluminum shell, packaging the core package by using butyl rubber, and aging the core package to obtain the electrolytic capacitor.
Performance detection
a. The electrolytes prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention were subjected to conductivity testing using a Shanghai Lei Ci DDSJ-308F bench conductivity tester, the test temperature was set to 35 ℃, and the test results are shown in the following table:
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Conductivity (s/cm) | 116.4 | 118.1 | 117.7 | 79.8 | 2.7×10 -3 |
As can be seen from the above table, the electrolyte prepared in examples 1 to 3 of the present invention has a high conductivity value and thus has good conductivity, while the conductive nano polymer added to the electrolyte prepared in comparative example 1 is non-modified nano polypyrrole and has general conductivity, so that the conductivity of the prepared electrolyte also shows general conductivity. The electrolyte prepared in comparative example 2 was not added with conductive nano polymer, and thus the conductivity was very poor.
b. Electrolytic capacitors prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention were prepared as test samples having a specification of 68uF/35V and a size of 6.3X17 mm, and the capacitance and capacity take-off of the samples were measured using a TH 2818-type automatic element analyzer, the frequency was set at 120Hz, and the test results were shown in the following table:
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Capacitance (uF) | 328.1 | 331.5 | 330.4 | 291.8 | 62.9 |
| Capacity yield (%) | 96.4 | 98.2 | 97.8 | 93.9 | 92.1 |
As can be seen from the above table, the capacitance value of the solid-liquid mixed electrolytic capacitor prepared in the embodiments 1 to 3 of the present invention is higher, because the solid-liquid mixed electrolytic capacitor prepared in the embodiments 1 to 3 of the present invention is impregnated with the solid-liquid mixed electrolytic solution, and the conductive nano polymer in the electrolytic solution has small particle size, so that the core can be loaded with more conductive nano polymer in the impregnation process, and the solid-liquid mixed electrolytic capacitor has higher capacitance due to the excellent conductivity of the conductive nano polymer.
The conductive nano polymer added to the solid-liquid mixed electrolyte used in the solid-liquid mixed electrolytic capacitor prepared in comparative example 1 is non-modified nano polypyrrole, resulting in poor conductivity of the electrolyte and thus inferior capacitance of the electrolytic capacitor to those prepared in examples 1 to 3.
The electrolytic capacitor prepared in comparative example 2 uses an electrolyte to which a conductive nano polymer is not added, and thus has very poor capacitance.
Since the additives used in the electrolytes prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention were the same, they all had good capacity take-off performance.
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 preparation method of the solid-liquid mixed electrolytic capacitor is characterized by comprising the following steps of:
step one: inserting an anode aluminum foil and a cathode carbon foil with oxide films on the surfaces and anode guide pins into electrolytic paper, and winding to form a core package;
step two: drying the core bag, spot-welding the core bag on an iron bar, and performing formation charging;
step three: drying the core bag subjected to the formation operation, immersing the core bag into a solid-liquid mixed electrolyte, and carrying out impregnation treatment;
step four: drying the impregnated core package, loading the core package into an aluminum shell, packaging the core package by using butyl rubber, and aging the core package to obtain a solid-liquid mixed electrolytic capacitor;
the solid-liquid mixed electrolyte comprises the following raw materials in parts by weight: 50-60 parts of main solvent, 10-20 parts of cosolvent, 4-8 parts of conductive nano polymer, 2-4 parts of ammonium formate, 1-3 parts of p-nitromethanol, 0.5-1 part of salicylic acid, 0.5-2 parts of boric acid and 0.1-0.5 part of phosphoric acid;
the main solvent is ethylene glycol; the cosolvent is any one of gamma-butyrolactone, sulfolane or dimethyl sulfoxide;
the conductive nano polymer is prepared by preparing nano polypyrrole by a microemulsion method and then grafting thiophene groups;
the preparation method of the conductive nano polymer comprises the following preparation steps:
step S1: dissolving sodium dodecyl sulfate in pure water, stirring for 30-60min, adding pyrrole monomer, stirring at 100-200rpm for 1-2h, reducing the rotation speed to 20-40rpm, adding glycerol, and stirring to form uniform solution;
step S2: dissolving ammonium persulfate in pure water to prepare an initiator solution, dripping the initiator solution into the uniform solution prepared in the step S1, stirring the solution at room temperature for 12 to 24 hours after the addition, centrifugally separating a solid product, washing the solid product by using acetone and the pure water, and carrying out vacuum drying to obtain nano polypyrrole;
step S3: dispersing nano polypyrrole in 65-75% ethanol water solution by volume fraction, adding 2-bromothiophene and alkaline catalyst, mixing, heating to 60-70 ℃, stirring for 12-24h, discharging, centrifuging to separate solid materials, washing, and vacuum drying to obtain the conductive nano polymer.
2. The method for manufacturing a solid-liquid mixed electrolytic capacitor according to claim 1, characterized in that the method for manufacturing a solid-liquid mixed electrolytic solution comprises the steps of:
the first step: mixing a main solvent and a cosolvent to form a uniform solution, raising the temperature to 60-80 ℃, adding the conductive nano polymer, and performing ultrasonic dispersion for 20-40min to obtain an electrolytic premix;
and a second step of: adding ammonium formate, p-nitromethanol, salicylic acid, boric acid and phosphoric acid into the electrolytic premix, stirring and mixing for 5-10min at 80-90 ℃, standing for 10-15min, and naturally cooling to obtain a solid-liquid mixed electrolyte.
3. The method for preparing a solid-liquid mixed electrolytic capacitor according to claim 1, wherein in step S1, the mass ratio of sodium dodecyl sulfate, pure water, pyrrole monomer and glycerin is 3-5:40-60:1:0.2-0.4.
4. The method for preparing a solid-liquid mixed electrolytic capacitor according to claim 1, wherein in step S2, the mass percentage concentration of the initiator solution is 4-8%.
5. The method for manufacturing a solid-liquid mixed electrolytic capacitor according to claim 1, wherein in step S2, the volume ratio of the initiator solution to the homogeneous solution is 1:4-6.
6. The method for preparing a solid-liquid mixed electrolytic capacitor according to claim 1, wherein in the step S3, the mass ratio of the nano polypyrrole to the 2-bromothiophene is 1:0.1-0.25.
7. The method for manufacturing a solid-liquid hybrid electrolytic capacitor according to claim 1, wherein in step S3, the alkaline catalyst is sodium hydroxide or potassium hydroxide.
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| CN110379627A (en) * | 2019-05-31 | 2019-10-25 | 益阳艾华富贤电子有限公司 | A kind of preparation process and solid-liquid mixed capacitor of solid-liquid mixed capacitor |
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| CN110379627A (en) * | 2019-05-31 | 2019-10-25 | 益阳艾华富贤电子有限公司 | A kind of preparation process and solid-liquid mixed capacitor of solid-liquid mixed capacitor |
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