CN110993344B - Solid-state aluminum electrolytic capacitor with high capacitance extraction rate and preparation method thereof - Google Patents
Solid-state aluminum electrolytic capacitor with high capacitance extraction rate and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 27
- 238000000605 extraction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 86
- 239000011888 foil Substances 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000004804 winding Methods 0.000 claims abstract description 7
- 229920005552 sodium lignosulfonate Polymers 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 17
- 230000001590 oxidative effect Effects 0.000 claims description 17
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 9
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 48
- 239000010408 film Substances 0.000 description 24
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- 108010093799 monoclonal nonspecific suppressor factor Proteins 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- WHRAZOIDGKIQEA-UHFFFAOYSA-L iron(2+);4-methylbenzenesulfonate Chemical compound [Fe+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 WHRAZOIDGKIQEA-UHFFFAOYSA-L 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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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
-
- 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
- H01G9/0029—Processes of manufacture
-
- 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
- H01G9/008—Terminals
- H01G9/012—Terminals specially adapted for solid capacitors
-
- 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
- H01G9/04—Electrodes or formation of dielectric layers thereon
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
A solid aluminum electrolytic capacitor with high capacitance extraction rate comprises a core package sealed in a shell, wherein the core package is formed by winding an anode foil, non-carbonized electrolytic paper and a cathode foil, and PEDOT (PEDOT: LS) doped by sodium lignosulfonate is filled between the anode foil and the cathode foil. LS films formed on the core package of the present invention are similar to conventional PEDOT: the conductivity of PSS films was comparable, but PEDOT: LS films were more uniform than PEDOT: the PSS film is much higher, so that the extraction rate and the leakage current performance of the capacitor are greatly improved.
Description
Technical Field
The invention relates to a solid-state aluminum electrolytic capacitor, in particular to a solid-state aluminum electrolytic capacitor with high capacitance extraction rate and a preparation method thereof.
Background
The electrolyte in the low-voltage solid capacitor enters the interior of the capacitor element through the processes of monomer impregnation, oxidant impregnation, polymerization and the like, and is filled with PEDT generated by chemical in-situ polymerization. Since the oxidant will be corrosive to the oxide film of the anode foil, the voltage withstanding value of the solid capacitor is low and the leakage current is large.
In order to solve the above problems, patent 201610302908.7, a novel solid-state aluminum electrolytic capacitor and a method for producing the same, proposes that gaps between the electrolytic paper and the anode foil and between the electrolytic paper and the cathode foil are filled with PEDOT: PSS. But the PEDOT: PSS has poor film thickness uniformity due to the low molecular weight of PEDOT, the high molecular weight of PSS, the existence of some sites on the PSS main chain which are not combined with PEDOT short chain, and the excessive amount of PSS in PEODS PSS system for maintaining the stability of dispersion liquid, which results in the poor uniformity of PEDOT PSS film; the lead-out ratio of the capacitor is not high, and the leakage current is large. Meanwhile, although PEDOT: the electrical conductivity of PSS is high, but for capacitors, the higher the electrical conductivity of the conductive polymer, the smaller the internal resistance of the solid-state aluminum electrolytic capacitor and the stronger the ability to withstand ripple current, so for PEDOT: PSS, there is also room for improvement in electrical conductivity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a solid aluminum electrolytic capacitor with uniform conductive polymer film thickness and high capacitance extraction rate and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a solid-state aluminum electrolytic capacitor with high capacitance extraction rate comprises a core package sealed in a shell, wherein the core package is formed by winding an anode foil, non-carbonized electrolytic paper and a cathode foil, and PEDOT (PEDOT: LS) doped with sodium lignosulfonate is filled between the anode foil and the cathode foil.
In the solid aluminum electrolytic capacitor with high capacity extraction rate, preferably, PEDOT is attached to the electrolytic paper, and PEDOT/LS, which is PEDOT doped with sodium lignosulfonate, is filled between the electrolytic paper and the anode foil and between the electrolytic paper and the cathode foil.
Preferably, when the PEDOT/LS dispersion liquid is prepared, the weight ratio of monomer EDOT to LS of the PEDOT is 2:1-1: 5.
In the solid aluminum electrolytic capacitor with high capacitance extraction, preferably, zinc phosphate is further doped in the PEDOT/LS thin film.
A preparation method of the solid-state aluminum electrolytic capacitor with high capacitance extraction rate comprises the following steps:
1) preparation of a dispersion of PEDOT and LS,
adding a predetermined amount of MNSF solid powder into deionized water, dissolving, then adding a predetermined amount of EDOT monomer, and emulsifying by vigorous stirring to 0.5-2 hours; the weight ratio of the EDOT monomer to the MNSF solid powder is 2:1-1: 5;
adding an oxidant which is 1-2 times of the molar equivalent of the EDOT monomer, and starting a polymerization reaction at room temperature-100 ℃; the time is 48 to 100 hours, and the stirring is kept in the reaction process;
2) winding the anode foil, the electrolytic paper and the cathode foil into a core package;
3) the core package was immersed in the PEDOT LS dispersion such that the core package was sufficiently impregnated with the PEDOT LS dispersion and then dried.
In the preparation method of the solid aluminum electrolytic capacitor with high capacitance extraction rate, the oxidant is aromatic ferric sulfonate; iron p-toluenesulfonate is preferred.
In the preparation method of the solid aluminum electrolytic capacitor with high capacitance extraction rate, preferably, the core wrap is impregnated with PEDOT, and a repeated impregnation method, a pressure impregnation method or a vacuum impregnation method is adopted when the LS dispersion liquid is used; wherein the impregnation method is repeated at normal temperature for 1-3 times, the first impregnation is followed by drying, and then the next impregnation is carried out, wherein the drying temperature is room temperature-120 ℃, and the drying time is 5-120 min; the pressure of the pressure impregnation is 0.1 to 1MPa, and the vacuum degree of the vacuum impregnation is 0.1 to 1 x 10-4Pa。
In the method for manufacturing the solid aluminum electrolytic capacitor with high capacitance extraction rate, each impregnation time of the repeated impregnation and the time of the pressure impregnation and the vacuum impregnation are preferably 0.5-12 h, and the concentration of the PEDT/PSS dispersion liquid is 0.1-30 wt%.
In the above method for manufacturing a solid aluminum electrolytic capacitor with a high capacitance extraction rate, preferably, PEDOT is attached to the electrolytic paper; the method for adhering PEDOT to the electrolytic paper comprises the following steps:
immersing the cut electrolytic paper into a mixed solution of a PEDOT monomer and an oxidant for impregnation for 0.5-60 min; wherein the concentration of the PEDOT monomer is 1-40 wt%, and the concentration of the oxidant is 10-70 wt%;
polymerizing the impregnated electrolytic paper for 1-48 h in an environment with the temperature of room temperature-170 ℃ to ensure that PEDOT is polymerized on the electrolytic paper.
Preferably, in the above method for manufacturing a solid aluminum electrolytic capacitor with a high capacitance extraction rate, the purification in step 1) includes the following steps: a, adding excessive sodium hydroxide and ammonia water into a PEDOT (lithium ion phosphate) LS dispersion liquid after polymerization reaction is finished, carrying out ultrasonic oscillation for 20min-1h, and then mechanically stirring for 12-36 h;
b, dialyzing the solution which is subjected to the step a in a dialysis bag with the molecular weight cutoff of 1000Da to remove small molecular inorganic matters and ammonia water;
c, filtering by adopting a filter membrane with the filtering diameter of 0.15-0.3 mu m to remove the PEDOT aggregate precipitate in the neutral state; obtaining the purified PEDOT LS dispersion liquid.
Compared with the prior art, the invention has the advantages that: LS films formed on the core package of the present invention are similar to conventional PEDOT: the conductivity of PSS films was comparable, but PEDOT: LS films were more uniform than PEDOT: the PSS film is much higher, which leads the extraction rate and the leakage current performance of the capacitor to be greatly improved.
Drawings
FIG. 1 is an electron micrograph of a PEDOT LS film from example 1.
FIG. 2 is a graph of PEDOT: electron microscopy scanning of PSS film.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
It should be particularly noted that when an element is referred to as being "fixed to, connected to or communicated with" another element, it can be directly fixed to, connected to or communicated with the other element or indirectly fixed to, connected to or communicated with the other element through other intermediate connecting components.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Example 1
A solid-state aluminum electrolytic capacitor with high capacitance extraction rate comprises a core package sealed in a shell, wherein the core package is formed by winding an anode foil, non-carbonized electrolytic paper and a cathode foil, and PEDOT (PEDOT: LS) doped by sodium Lignosulfonate (LS) is filled between the anode foil and the cathode foil.
In the present invention, since the conductivity of the PEDOT-LS film is low compared to PEDOT; therefore, to reduce the ESR of the capacitor, PEDOT, which is PEDOT: LS doped with sodium lignosulfonate, may be attached to the electrolytic paper, and between the electrolytic paper and the anode foil and between the electrolytic paper and the cathode foil.
As shown in FIG. 2, the PEDOT: PSS is a mixture of rigid PEDOT chains and flexible PSS chains, and the dispersion tends to separate from the PSS during the molding process to form stable, continuous phases, respectively, to maintain thermodynamic equilibrium. The PEDOT PSS also causes uneven dispersion of the PEDOT due to the inherent phase separation characteristic, namely, a large amount of PSS enriched areas exist in the PEDOT PSS film, a large area of PSS insulation areas exist in the film, and the PSS is insulated, so that the uniformity of the resistance of the film is reduced.
In the present invention, since some reducing units are present in LS, for example, unsaturated carbon-carbon double bonds, phenols, and the like; during the oxidative polymerization of EDOT, it can be oxidized by the oxidizer to participate in the reaction. The unsaturated carbon-carbon double bond and phenol in the LS endow the LS with high reactivity, the LS has the functions of a doping agent and a dispersing agent when the EDOT is reacted and polymerized, the LS is contacted and adsorbed with the EDOT, the hydrophilic group of the LS faces outwards, the hydrophobic group of the LS faces towards EDOT liquid drops, and the LS is stably dispersed in an aqueous solution system. Because the oxidative polymerization reaction of the EDOT is also a double-bond opening type coupling reaction, in the oxidative polymerization reaction process of the EDOT, the LS not only plays a role of a doping agent and a dispersing agent, but also can be coupled with the unsaturated carbon-carbon double bond and the phenol group of the thiophene to a certain extent to form a cross-linked network formed by mutually penetrating the LS and the PEDOT. It can be seen that the uniformity of the PEDOT: LS film formed in the core package is better. As shown in fig. 1, the LS has a smaller aggregate size due to the small molecular weight of LS, and the PEDOT is smaller than the phase separation scale of the LS film; and the arrangement of the PEDOT aggregates on the surface of the PEDOT/LS film is very uniform, so that the electrical uniformity of the PEDOT/LS film is better.
In this example, zinc phosphate was further doped in the PEDOT: LS thin film. The amount of zinc phosphate is one fifth to one third of the amount of LS. Since the pH of the LS solution is 2-6, in order to prevent the corrosion of the anode oxide film (aluminum oxide) by LS in the PEDOT: LS film, after the zinc phosphate is added, the acidity of the LS is weakened in the film forming process of the PEDOT: LS film, so that the corrosion of the oxide film is reduced after the film forming.
A preparation method of a solid-state aluminum electrolytic capacitor with high capacitance extraction rate comprises the following steps:
1) preparation of a dispersion of PEDOT and LS,
will preAdding quantitative MNSF solid powder into deionized water, and dissolving; then adding predetermined amount of EDOT monomer and zinc phosphate, and stirring and emulsifying vigorously for 1 hour; the weight ratio of the EDOT monomer to the MNSF solid powder is 1: 5;
adding an oxidant which is 1.4 times of the molar equivalent of the EDOT monomer, and starting a polymerization reaction at the room temperature of-100 ℃; the time is 48 to 100 hours, and the stirring is kept in the reaction process;
step (ii) ofAfter the reaction is finished, purifying to obtain zinc phosphate doped PEDOT LS dispersion liquid;
2) winding the anode foil, the electrolytic paper and the cathode foil into a core package;
3) the core package was immersed in the zinc phosphate doped PEDOT: LS dispersion such that the core package was sufficiently impregnated with the zinc phosphate doped PEDOT: LS dispersion and then dried.
In this embodiment, the oxidant is iron p-toluenesulfonate.
In the embodiment, when the core package is impregnated into the PEDOT, the LS dispersion liquid adopts a repeated impregnation method, a pressure impregnation method or a vacuum impregnation method; wherein the impregnation method is repeated at normal temperature, the impregnation frequency is 3 times, the first impregnation is firstly carried out, then the next impregnation is carried out, the drying temperature is between room temperature and 120 ℃, and the drying time is 5 to 120 min; the pressure of the pressure impregnation is 0.9MPa, and the vacuum impregnation degree is0.1~1×10-4Pa。
In the above method for producing a solid aluminum electrolytic capacitor having a high extraction rate of capacitance, it is preferable that the impregnation time and the pressure impregnation and vacuum impregnation time are both 5 hours for each repeated impregnation, and the concentration of the dispersion of PEDT and PSS is 20 wt%.
In this example, PEDOT was attached to the electrolytic paper; the method for adhering PEDOT to the electrolytic paper comprises the following steps:
immersing the cut electrolytic paper into a mixed solution of a PEDOT monomer and an oxidant for impregnation for 0.5-60 min; wherein the concentration of the PEDOT monomer is 1-40 wt%, and the concentration of the oxidant is 10-70 wt%;
polymerizing the impregnated electrolytic paper for 1-48 h in an environment with the temperature of room temperature-170 ℃ to ensure that PEDOT is polymerized on the electrolytic paper.
In this embodiment, the purification in step 1) includes the following steps: a, adding excessive sodium hydroxide and ammonia water into a PEDOT (lithium ion phosphate) LS dispersion liquid after polymerization reaction is finished, carrying out ultrasonic oscillation for 20min-1h, and then mechanically stirring for 12-36 h;
b, dialyzing the solution which is subjected to the step a in a dialysis bag with the molecular weight cutoff of 1000Da to remove small molecular inorganic matters and ammonia water;
c, filtering by adopting a filter membrane with the filtering diameter of 0.15-0.3 mu m to remove the PEDOT aggregate precipitate in the neutral state; obtaining the purified PEDOT LS dispersion liquid.
The solid aluminum electrolytic capacitor with high capacitance extraction rate of the embodiment is improved by more than 6 percent compared with the traditional solid aluminum electrolytic capacitor using PEDOT (Poly ethylene glycol Ether-styrene) PSS (Polyacrylonitrile-styrene) conducting polymer; and the leakage current of the capacitor is small due to the uniform internal resistance.
Claims (5)
1. A preparation method of a solid-state aluminum electrolytic capacitor with high capacitance extraction rate is characterized by comprising the following steps: the method comprises the following steps:
1) preparation of a dispersion of PEDOT and LS,
adding LS solid powder into deionized water, dissolving, adding EDOT monomer, and emulsifying for 0.5-2 hr; the weight ratio of the EDOT monomer to the LS solid powder is 2:1-1: 5;
adding an oxidant which is 1-2 times of the molar equivalent of the EDOT monomer, and starting a polymerization reaction at room temperature-100 ℃; the time is 48 to 100 hours, and the stirring is kept in the reaction process;
step (ii) ofAfter the reaction is finished, purifying to obtain PEDOT LS dispersion liquid; in said step 1), zinc phosphate is added in an amount of one fifth to one third based on the weight of LS before the polymerization reaction is started
2) Winding the anode foil, the electrolytic paper and the cathode foil into a core package;
3) immersing the core bag into PEDOT LS dispersion liquid, so that the core bag is fully immersed with the PEDOT LS dispersion liquid and then dried;
the core package is formed by winding an anode foil, non-carbonized electrolytic paper and a cathode foil, and PEDOT (PEDOT: LS) doped by sodium lignosulfonate is filled between the anode foil and the cathode foil.
2. The method for manufacturing a solid-state aluminum electrolytic capacitor with high capacitance extraction according to claim 1, characterized in that: the oxidant is aromatic ferric sulfonate.
3. The method for manufacturing a solid-state aluminum electrolytic capacitor with high capacitance extraction according to claim 1, characterized in that: the core bag is impregnated with PEDOT, wherein a repeated impregnation method, a pressure impregnation method or a vacuum impregnation method is adopted when the LS dispersion liquid is used; wherein the impregnation method is repeated at normal temperature for 1-3 times, the first impregnation is followed by drying, and then the next impregnation is carried out, wherein the drying temperature is room temperature-120 ℃, and the drying time is 5-120 min; the pressure of the pressure impregnation is 0.1 to 1MPa, and the vacuum degree of the vacuum impregnation is 0.1 to 1 × 10-4Pa; the impregnation time of each impregnation repeated and the pressure impregnation and vacuum impregnation time are both 0.5-12 h, and the concentration of the PEDOT/PSS dispersion liquid is 0.1-30 wt%.
4. The method for manufacturing a solid-state aluminum electrolytic capacitor with high capacitance extraction according to claim 1, characterized in that: PEDOT is attached to the electrolytic paper; the method for adhering PEDOT to the electrolytic paper comprises the following steps:
immersing the cut electrolytic paper into a mixed solution of a PEDOT monomer and an oxidant for impregnation for 0.5-60 min; wherein the concentration of the PEDOT monomer is 1-40 wt%, and the concentration of the oxidant is 10-70 wt%;
5. The method for manufacturing a solid-state aluminum electrolytic capacitor with high capacitance extraction according to claim 1, characterized in that: the purification in the step 1) comprises the following steps: a, adding excessive sodium hydroxide and ammonia water into a PEDOT (lithium ion phosphate) LS dispersion liquid after polymerization reaction is finished, carrying out ultrasonic oscillation for 20min-1h, and then mechanically stirring for 12-36 h;
b, dialyzing the solution which is subjected to the step a in a dialysis bag with the molecular weight cutoff of 1000Da to remove small molecular inorganic matters and ammonia water;
c, filtering by adopting a filter membrane with the filtering diameter of 0.15-0.3 mu m to remove the PEDOT aggregate precipitate in the neutral state; obtaining the purified PEDOT LS dispersion liquid.
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