CN118538543A - Semi-solid aluminum electrolytic capacitor and preparation method thereof - Google Patents
Semi-solid aluminum electrolytic capacitor and preparation method thereof Download PDFInfo
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- CN118538543A CN118538543A CN202410704688.5A CN202410704688A CN118538543A CN 118538543 A CN118538543 A CN 118538543A CN 202410704688 A CN202410704688 A CN 202410704688A CN 118538543 A CN118538543 A CN 118538543A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 58
- 239000007787 solid Substances 0.000 title claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000002608 ionic liquid Substances 0.000 claims abstract description 60
- 239000011888 foil Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical class CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 organic acid amidine salt Chemical class 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 25
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
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- RGHNJXZEOKUKBD-NRXMZTRTSA-N (2r,3r,4r,5s)-2,3,4,5,6-pentahydroxyhexanoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-NRXMZTRTSA-N 0.000 claims description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
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- 239000000178 monomer Substances 0.000 description 4
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
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- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- LOSWWGJGSSQDKH-UHFFFAOYSA-N 3-ethoxypropane-1,2-diol Chemical compound CCOCC(O)CO LOSWWGJGSSQDKH-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
A semi-solid aluminum electrolytic capacitor comprises a core pack; the core package comprises an anode foil, electrolytic paper and a cathode foil, wherein the electrolytic paper is arranged between the anode foil and the cathode foil, a conductive high polymer is formed between the anode foil and the cathode foil, and the core package is impregnated with ionic liquid after the conductive high polymer is formed on the core package; the ionic liquid comprises chlorinated 1-allyl-3-methylimidazole. The method for improving the performance of the polymer electrode by taking the high-conductivity ionic liquid as the additive can manufacture the semi-solid capacitor with the characteristics of high reliability, high capacity, high temperature resistance, low impedance, small leakage current and the like.
Description
Technical Field
The invention relates to an aluminum electrolytic capacitor, in particular to a semi-solid aluminum electrolytic capacitor and a preparation method thereof.
Background
Under the push of the rapid development of wearable electronic equipment, the development and preparation of energy storage equipment with light weight, small volume, high energy density and power density and stable performance become a big hot spot of current research. The semi-solid capacitor is considered as a promising energy storage device because of the advantages of high charge and discharge speed, high cycle stability, high safety, good electrochemical performance under different forms, and the like, and the advantages and disadvantages of the semi-solid capacitor performance depend on the performance of the core components (electrodes and electrolyte). The semi-solid capacitor requires the advantages of miniaturization, high capacity, low equivalent series resistance ESR, high ripple current resistance, long service life, stable performance and the like.
The electrolyte of the liquid capacitor device is liquid electrolyte, and mainly comprises an ethylene glycol system and the like. The electrolyte of the semi-solid capacitor is composed of gel-shaped conductive polymer. The conductive polymer has much higher conductivity than liquid electrolyte, and has the advantages of low ESR, but weak repairing capability to the defect part of the anodic oxide film. Therefore, when the semi-solid aluminum electrolytic capacitor is used in a high-temperature working environment of 85-150 ℃ for a long time, LC is likely to be increased, and even short circuit is likely to be caused. Semi-solid capacitors are currently mainly used in the low voltage range, essentially operating below 25V. The performance is poor in terms of high voltage, while ionic liquids can operate at higher voltages. In response to such market demands, a semi-solid electrolytic capacitor has been developed in which a conductive solid electrolyte made of a conductive polymer is filled in a capacitor core pack and modified with an Ionic Liquid (IL).
Electrolyte material selection: highly conductive IL with highly conductive polymeric solid state electrolytes. In order to obtain the high molecular conductive polymer layer, the method must be formed by a chemical overlap method. The core is made up by immersing the core in monomer and oxidant solution containing thiophene or its derivative, pyrrole or its derivative and aniline or its derivative, and then making chemical superposition reaction in high-temp. environment so as to obtain the high-molecular conductive polymer layer with a certain thickness. Because the monomer and oxidant solution belongs to a strong acid solution, the material component contains iron compounds or persulfates, the core is soaked and then dried at high temperature, the core is covered with residues of impurities, and how to remove the residues is an important engineering. The second method is to impregnate a dispersion liquid formed by dispersing conductive polymer particles or powder, which are formed by the coexistence of polymer doping having an average molecular weight of 5000-50000 and low-molecular doping having an average molecular weight of 500 or less, in water. The application method of the invention comprises the following steps:
Firstly, the core is contained in a mixed aqueous solution containing thiophene or an inductor thereof, impurities remained in the core are removed by an oxidation superposition method, the treatment temperature is 30-45 ℃, the treatment time is 10-30 min, and then the core is washed and dried in pure water, so that a high-molecular conductive polymer layer with a certain thickness is obtained.
In the second method, the core is immersed in a dispersion of an aqueous dispersion solution containing polyethylene 3,4 ethylenedioxythiophene or the like, so that the core pack has conductive solid particles or coagulated particles therein to form a conductive solid layer. The dispersion liquid has the impregnation vacuum degree of-50 to-80 KPa, and the drying condition is as follows: the temperature is 100-200 ℃ and the time is 30-120 min. Repeating the impregnating step 3-5 times to form a high polymer conductive polymer layer with a certain thickness on the aluminum electrode foil.
IL is composed of a polymer backbone and Ionic Liquid Monomers (ILMs). Certain specific properties of ILs, ranging from monomers to oligomers to high molecular mass polymers, such as negligible vapor pressure, thermal stability, non-flammability, high ionic conductivity, and broad electrochemical stability window, can be transferred into the polymer chain. In addition, the designability of ILs and the selectivity of polymer segments are more abundant in their application in electrochemistry.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a high-reliability high-temperature-resistant long-life semi-solid capacitor based on ionic liquid and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a semi-solid aluminum electrolytic capacitor comprises a core pack; the core package comprises an anode foil, electrolytic paper and a cathode foil, wherein the electrolytic paper is arranged between the anode foil and the cathode foil, a conductive high polymer is formed between the anode foil and the cathode foil, and the core package is impregnated with ionic liquid after the conductive high polymer is formed on the core package; the ionic liquid comprises chlorinated 1-allyl-3-methylimidazole.
In the above semi-solid aluminum electrolytic capacitor, preferably, an organic acid amidine salt and/or an organic acid pyridinium salt as a solute is added to the ionic liquid.
In the above semi-solid aluminum electrolytic capacitor, preferably, the core comprises a treatment liquid impregnated before the ionic liquid is impregnated; the treatment fluid comprises a solvent and a solute, wherein the solvent comprises a water-based high polymer material with a characteristic of difficult volatilization, an organic solvent with a boiling point below 100 ℃, an organic solvent with a boiling point above 150 ℃ and water, and the solute is one or more of an organic acid compound and an inorganic acid compound.
In the above semi-solid aluminum electrolytic capacitor, preferably, the water-based polymer material with a characteristic of difficult volatilization includes one or more of polyethylene alkylene glycol, polyvinyl alcohol, polyethylene glycol glycerol ethyl ether, polyethylene glycol diglycol ethyl ether, polyethylene glycol sorbitol ethyl ether, polyethylene glycol, polybutylene glycol, polyethylene glycol, and polyethylene oxide.
In the above semi-solid aluminum electrolytic capacitor, preferably, the organic solvent having a boiling point of 100 ℃ or less includes methanol or ethanol; the organic solvent with the boiling point of above 150 ℃ comprises one or more of ethylene glycol, propylene glycol, mannitol, glycerol, sulfolane, butanediol, diethylene glycol and gamma-butyrolactone.
Preferably, the solute of the semi-solid aluminum electrolytic capacitor comprises one or more of phosphoric acid, boric acid, benzoic acid, adipic acid, azelaic acid, sebacic acid, isophthalic acid, phthalic acid, maleic acid, benzenesulfonic acid and citric acid.
A preparation method of a semi-solid aluminum electrolytic capacitor comprises the following steps;
1) Winding the anode foil, the electrolytic paper and the cathode foil into a core package;
2) The core of the step) is immersed into a chemical solution and dried, so that oxide film defects on the surface of the anode foil are repaired;
3) Forming a conductive high molecular polymer before the anode foil and the cathode foil of the core package;
4) Impregnating an ionic liquid, wherein the ionic liquid comprises 1-allyl-3-methylimidazole chloride;
5) And (3) packaging the core package which completes the step 4) in a shell to form the aluminum electrolytic capacitor.
In the above method for preparing a semi-solid aluminum electrolytic capacitor, preferably, the ionic liquid in the step 4) is added with organic acid amidine salt and/or organic acid pyridinium salt as a solute.
In the above method for manufacturing a semi-solid aluminum electrolytic capacitor, preferably, between the steps 3) and 4), the core is immersed in the treatment liquid and dried; the treatment fluid comprises a solvent and a solute, wherein the solvent comprises a water-based high polymer material with a characteristic of difficult volatilization, an organic solvent with a boiling point below 100 ℃, an organic solvent with a boiling point above 150 ℃ and water, and the solute is one or more of an organic acid compound and an inorganic acid compound.
In the above method for manufacturing a semi-solid aluminum electrolytic capacitor, preferably, the conductive polymer in the step 3) includes one of polythiophene or a derivative thereof, polypyrrole or a derivative thereof, and polyaniline or a derivative thereof.
Compared with the prior art, the invention has the advantages that: the method for improving the performance of the polymer electrode by taking the high-conductivity ionic liquid as the additive can manufacture the semi-solid capacitor with the characteristics of high reliability, high capacity, high temperature resistance, low impedance, small leakage current and the like.
Detailed Description
The present invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating understanding of the present invention, but the scope of protection of the present invention is not limited to the specific embodiments described below.
It will be understood that when an element is referred to as being "fixed, affixed, connected, or in communication with" another element, it can be directly fixed, affixed, connected, or in communication with the other element or intervening elements may be present.
Unless defined otherwise, all technical and scientific terms 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 be limiting of the scope of the present invention.
The invention provides a semi-solid aluminum electrolytic capacitor, which comprises a core package; the core package is formed by winding anode foil, electrolytic paper and cathode foil, the electrolytic paper is arranged between the anode foil and the cathode foil, conductive high polymer is formed between the anode foil and the cathode foil, and the core package is impregnated with Ionic Liquid (IL) after the conductive high polymer is formed. The ionic liquid comprises chlorinated 1-allyl-3-methylimidazole; the ionic liquid may be added with an organic acid amidine salt and/or an organic acid pyridinium salt as a solute.
In the invention, the ionic liquid has higher ionic conductivity; 25. when the polymer is at the temperature of 10 -3 S·cm-1 ℃, the polymer can provide electronic conductivity, and simultaneously serve as a plasticizer, so that the glass transition temperature of the polymer is reduced, an amorphous area is increased, and the conductivity is improved. The ionic liquid body has an electrochemical window as wide as 5V, and can avoid side reactions of direct contact between the anodic aluminum oxide and the electrolyte. The ionic liquid has high safety performance, high thermal stability and nonflammability. The ionic liquid is not easy to volatilize, and has hydrogen bond interaction with alumina and electrolyte. Especially under the conditions of high temperature and high pressure, the instability caused by liquid flow can be avoided, the effective contact in a semi-solid state can be ensured, and the circulation performance is maintained; according to the invention, the microstructure of the polymer is changed by adding the ionic liquid, and the charge storage performance and the cycle stability of the polymer are obviously improved by improving the effective specific surface area of the polymer and the electrode.
In the present invention, the conductive high molecular polymer includes one of polythiophene or a derivative thereof, polypyrrole or a derivative thereof, polyaniline or a derivative thereof.
According to the invention, the microstructure of the polymer is changed by adding the ionic liquid, so that the charge storage performance and the cycle stability of the polymer are improved, and the performances of the conjugated polymer can be improved by different chemical modifications, so that the characteristics required by technical application are met. Polymer electrolytes are a key driving factor for electrochemical capacitors. Ionic Liquids (IL) have good ionic conductivity, low volatility and a broad electrochemical potential window. The ionic liquid can also be used as an ionic conductor and a plasticizer to be added into the polymer electrolyte, so that the defect part of the anodic oxide film can be well protected.
In the present invention, the pore walls of the anode foil surface contain a mixture of Al-O surface sites that can bind to the cations and anions of 1-allyl-3-methylimidazole chloride, and the C2-H groups on the imidazole ring can form weak hydrogen bonds with lewis bases, so that these groups are likely to form similar types of interactions with the negatively charged surface sites on the pore walls to act as lewis acid binding sites for IL, which can alter or redirect cation-anion stacking and alter ion-ion distance. The local coordination environment is regulated, the interference of pressure change is relieved, and the defect part of the anodic oxide film is well protected.
In the invention, the ionic liquid has good wettability, and the ionic liquid is easier to permeate into the gaps of the conductive high polymer inside the core bag. The ionic liquid has good compatibility and good impregnation permeability, and the ionic liquid surrounds the conductive high-molecular polymer after the ionic liquid is impregnated into the core bag, which is equivalent to protecting and preventing cracking and decomposition of the conductive high-molecular polymer. Even under the high temperature condition, the electrolyte can be closely contacted with the electrolyte modified by the ionic liquid due to the excellent semi-solid contact property, so that the electrolyte and the anodic aluminum oxide can be closely adhered to each other, and the semi-solid electrolytic capacitor with low impedance characteristic can be obtained.
The semi-solid electrolyte with the protective layer is prepared by adopting the ionic liquid and the traditional polymer basal layer, so that the flexibility of the traditional polymer chain segment can be improved, and the migration of ions can be increased.
An ionic liquid and a conventional polymeric base layer are used to prepare a semi-solid electrolyte with a protective layer. The strong electronegative Cl atoms contained in the anionic groups of the IL can form stronger H bond action with H atoms in the side chain hydroxyl groups of the conductive high-molecular polymer. So that the mechanical property of the interface is improved. When bending deformation occurs, a part of energy is consumed by a polymer molecular chain, so that the flexibility of a traditional polymer chain segment is improved.
In the present invention, the treatment liquid contains a polyethylene alkylene glycol having a characteristic of being difficult to volatilize or a dielectric thereof, and the capacitor can ensure a good short-circuit resistance while suppressing an increase in LC even when used in a high temperature environment (maximum use temperature) of 85 to 150 ℃ over a guaranteed lifetime. The treatment liquid contains organic solvents with different boiling points, and after the core is immersed in the treatment liquid, the electrolyte of the conductive polymer film layer is more uniform and stabilized when the conductive polymer film which is permeated into the treatment liquid is dried.
The invention also provides a preparation method of the semi-solid aluminum electrolytic capacitor, which comprises the following steps of;
1) Winding the anode foil, the electrolytic paper and the cathode foil into a core package;
2) The core of the step) is immersed into a chemical solution and dried, so that oxide film defects on the surface of the anode foil are repaired;
3) Forming a conductive high molecular polymer before the anode foil and the cathode foil of the core package;
4) Impregnating an ionic liquid, wherein the ionic liquid comprises 1-allyl-3-methylimidazole chloride;
5) And (3) packaging the core package which completes the step 4) in a shell to form the aluminum electrolytic capacitor.
In the invention, the ionic liquid in the step 4) is added with organic acid amidine salt and/or organic acid pyridinium salt serving as solute.
In the present invention between step 3) and step 4), the core is immersed in the treatment liquid and dried; the treatment fluid comprises a solvent and a solute, wherein the solvent comprises a water-based polymer material with a characteristic of difficult volatilization, an organic solvent with a boiling point below 100 ℃, an organic solvent with a boiling point above 150 ℃ and water, and the solute is one or more of an organic acid compound and an inorganic acid compound.
In the invention, the water-based polymer material with the characteristic of difficult volatilization comprises one or more of polyethylene alkylene glycol, polyvinyl alcohol, polyethylene glycol glycerol ether, polyethylene glycol diglycol ether, polyethylene glycol sorbitol ether, polyethylene glycol, polybutylene glycol, polyethylene glycol and polyethylene oxide.
In the invention, the organic solvent with the boiling point below 100 ℃ comprises methanol or ethanol; the organic solvent with the boiling point of above 150 ℃ comprises one or more of ethylene glycol, propylene glycol, mannitol, glycerol, sulfolane, butanediol, diethylene glycol and gamma-butyrolactone.
In the present invention, the solute comprises one or more of phosphoric acid, boric acid, benzoic acid, adipic acid, azelaic acid, sebacic acid, isophthalic acid, phthalic acid, maleic acid, benzenesulfonic acid, and citric acid.
In the aluminum electrolytic capacitor, an aluminum oxide film formed on the surface of an anode foil is alpha-Al 2O3, and the aluminum oxide film cannot react with acid at normal temperature; however, when the electric field distribution is uneven in the use process of the aluminum electrolytic capacitor, the local oxide film may generate leakage current due to overhigh voltage, so that the local oxide film generates heat; after the temperature rises, the aluminum oxide film is corroded by acid decomposed by the dopant, such as sulfuric acid generated by p-toluenesulfonic acid, causing problems of electric leakage, short circuit failure and the like. The organic acid and the inorganic acid compound are added into the treatment liquid, so that the oxygen ion can be provided for repairing the anodic oxide film, and the problems of electric leakage, short circuit failure and the like caused by acid decomposed by the doping agent, such as sulfuric acid generated by p-toluenesulfonic acid, corroding the alumina film in the charge-discharge cycle process of the capacitor are avoided.
In the present invention, between step 3) and step 4), the core is immersed in the treatment liquid and dried; the components of the treatment liquid comprise solvent and solute, wherein the solvent comprises water-based polymer material with difficult volatilizing property, organic solvent with boiling point below 100 ℃, organic solvent with boiling point above 150 ℃ and water, and the solute is one or more of organic acid compound and inorganic acid compound.
In the present invention, the conductive high molecular polymer in the step 3) includes one of polythiophene or a derivative thereof, polypyrrole or a derivative thereof, polyaniline or a derivative thereof.
Example 1
The embodiment comprises the following steps:
A1, manufacturing a core package, cutting an anode foil, a negative foil and electrolytic paper according to design dimensions, riveting an anode guide pin and a cathode guide pin on the anode foil and the cathode foil respectively, and winding the anode foil, the cathode foil and the electrolytic paper into an elliptic cylinder and a cylindrical core package;
a2, a first impregnation stage, wherein the core contains low-pressure formation liquid of an adipic acid impregnation system, and the anode lead pin and the cathode lead pin are applied with 110V voltage, the current density is 0.05mA/pcs, so that the oxide film defect caused by cutting and nailing the surface of the anode foil is repaired.
A3, a second impregnation stage, wherein the core is immersed in a dispersion liquid of a dispersion aqueous solution containing polyethylene 3,4 ethylenedioxythiophene, so that the conductive high-molecular polymer solid particles or solidification bodies thereof are contained in the core package to form a conductive high-molecular polymer layer. The dispersion liquid has the impregnation vacuum degree of-55 to-65 KPa and the drying condition: the temperature is 125 ℃ and the time is 45min. Repeating the impregnating step 3-5 times to form a conductive high polymer layer with a certain thickness on the aluminum electrode foil. The dispersion comprises, in weight percent, 2% of polyethylene dioxythiophene, 4% of polystyrene sulphonic acid having an average molecular weight of 50000, 0.5% of toluene sulphonic acid.
And A4, a third impregnation stage, wherein the core contains an impregnation treatment liquid, and the treatment liquid is easier to permeate into gaps of the conductive high polymer layer serving as the solid electrolyte in the core bag because of good wettability of the treatment liquid, and the dielectric oxide film on the surface of the anode foil and in the etching holes is further repaired by the action of the treatment liquid, so that the dielectric oxide film on the surface of the anode foil and in the etching holes is more compact. The vacuum degree of the treatment fluid is-55 to-65 KPa, and the drying conditions are as follows: the temperature is 200 ℃ and the time is 30min. The treatment fluid comprises polyethylene glycol with molecular weight of 200, and comprises polyethylene glycol (PEG) 35%, ethylene Glycol (EG) 15%, gamma-butyl lactone 10% (GBL), ethanol 15%, water 20% and phthalic acid 5% by weight.
And A5, a fourth impregnation stage, wherein the core comprises an ion liquid, the impregnation vacuum degree of the ion liquid is-55 to-65 KPa, and the time is 5min. The ionic liquid is chloridized 1-allyl-3-methylimidazole (AMIMCl) ionic liquid, and the mass ratio of the ionic liquid to the electrolyte membrane is 1:4.
A6, encapsulating the core package subjected to the fourth impregnation stage into an aluminum shell.
Example 2
The steps and principles of this embodiment are basically the same as those of the first embodiment, except for the following steps.
The dispersion in step A3 of this example comprises, in weight percent, 2% of polyethylene dioxythiophene, 4% of polystyrene sulphonic acid having an average molecular weight of 100000, 0.5 of toluene sulphonic acid.
The treatment fluid in example A4 included polyethylene glycol having a molecular weight of 200, polyethylene glycol (PEG) 35%, ethylene Glycol (EG) 15%, gamma-butyrolactone 10% (GBL), ethanol 15%, water 20% and phthalic acid 5% by weight.
The ionic liquid in this example A5 was a 1-allyl-3-methylimidazole chloride (AMIMCl) ionic liquid; the mass ratio of the ionic liquid to the electrolyte membrane is 1:4.
Comparative example 1
An electrolytic capacitor was produced in the same manner as in the rest of the procedure except that toluene sulfonic acid was removed from the dispersion of example 1 and the dispersion was impregnated.
Comparative example 2
An electrolytic capacitor was produced in the same manner as in the rest of the procedure except that the dispersion of example 2 was immersed in the dispersion after removing polystyrene sulfonic acid.
Comparative example 3
An electrolytic capacitor was produced in the same manner as in the other steps except that the ionic liquid impregnation step in example 1 was removed.
Comparative example 4
An electrolytic capacitor was produced in the same manner as in the other steps except that the ionic liquid impregnation step in example 2 was removed.
The capacitors produced by the above method were all numbered 20pcs of each experimental sample, and the experimental data were the average of the 20pcs of the test. Initial characteristic parameters were measured and CAP, DF, ESR, LC, the results are shown in Table I; all the experimental samples were subjected to reflow test (1 time) and the characteristic parameters after the reflow test were tested, and the results were shown in Table II as the reflow test was performed according to the heat resistance test conditions in IEC60068-2-58 (2004). (remark: ESR:100KHz test; CAP:120Hz test). The sample after the reflow soldering test is subjected to a 125 ℃ high-temperature load reliability life test, and the electrical parameters are shown in a table III; the electrical parameters of the test are shown in Table IV.
From the above experimental findings, it can be seen that: the initial capacitor characteristic parameters of the first and second embodiments and the first and second comparative embodiments have little difference, and the initial capacitor characteristic parameters of the first and second embodiments 1 and 2 have little ESR/LC and little CAP/DF difference compared with the comparative embodiments 3 and 4; the reflow test (1 time) is carried out, and the characteristic parameters after the reflow test are tested, so that the capacitor characteristic parameters of the embodiment 1 and the embodiment 2 have obvious advantages, and particularly the ESR after the reflow test; the capacitors of example 1 and example 2 have significant advantages in the analysis of the electrical characteristic parameters of the test sample 105 ℃/125 ℃ high temperature load reliability life test.
By using the high-conductivity ionic liquid as the additive to improve the performance of the polymer electrode, the semi-solid capacitor with the characteristics of high reliability, high capacity, high ripple current resistance, high temperature resistance, low impedance, small leakage current and the like can be provided.
Claims (10)
1. A semi-solid aluminum electrolytic capacitor comprises a core pack; the method is characterized in that: the core package comprises an anode foil, electrolytic paper and a cathode foil, wherein the electrolytic paper is arranged between the anode foil and the cathode foil, a conductive high polymer is formed between the anode foil and the cathode foil, and the core package is impregnated with ionic liquid after the conductive high polymer is formed on the core package; the ionic liquid comprises chlorinated 1-allyl-3-methylimidazole.
2. The semi-solid aluminum electrolytic capacitor as claimed in claim 1, wherein: the ionic liquid is added with organic acid amidine salt and/or organic acid pyridinium salt serving as solutes.
3. The semi-solid aluminum electrolytic capacitor as claimed in claim 1, wherein: the core is impregnated with a treatment liquid prior to impregnation with the ionic liquid; the treatment fluid comprises a solvent and a solute, wherein the solvent comprises a water-based high polymer material with a characteristic of difficult volatilization, an organic solvent with a boiling point below 100 ℃, an organic solvent with a boiling point above 150 ℃ and water, and the solute is one or more of an organic acid compound and an inorganic acid compound.
4. A method for manufacturing a semi-solid aluminum electrolytic capacitor according to claim 3, wherein: the water-based polymer material with the characteristic of difficult volatilization comprises one or more of polyethylene alkylene glycol, polyvinyl alcohol, polyethylene glycol glycerol ether, polyethylene glycol diglycol ether, polyethylene glycol sorbitol ether, polyethylene glycol, polybutylene glycol, polyethylene glycol and polyethylene oxide.
5. A method for manufacturing a semi-solid aluminum electrolytic capacitor according to claim 3, wherein: the organic solvent with the boiling point below 100 ℃ comprises methanol or ethanol; the organic solvent with the boiling point of above 150 ℃ comprises one or more of ethylene glycol, propylene glycol, mannitol, glycerol, sulfolane, butanediol, diethylene glycol and gamma-butyrolactone.
6. A method for manufacturing a semi-solid aluminum electrolytic capacitor according to claim 3, wherein: the solute comprises one or more of phosphoric acid, boric acid, benzoic acid, adipic acid, azelaic acid, sebacic acid, isophthalic acid, phthalic acid, maleic acid, benzenesulfonic acid and citric acid.
7. A preparation method of a semi-solid aluminum electrolytic capacitor is characterized in that: comprises the following steps of;
1) Winding the anode foil, the electrolytic paper and the cathode foil into a core package;
2) The core of the step) is immersed into a chemical solution and dried, so that oxide film defects on the surface of the anode foil are repaired;
3) Forming a conductive high molecular polymer before the anode foil and the cathode foil of the core package;
4) Impregnating an ionic liquid, wherein the ionic liquid comprises 1-allyl-3-methylimidazole chloride;
5) And (3) packaging the core package which completes the step 4) in a shell to form the aluminum electrolytic capacitor.
8. The method for manufacturing a semi-solid aluminum electrolytic capacitor as claimed in claim 7, wherein: and 3) adding organic acid amidine salt and/or organic acid pyridinium salt serving as solutes into the ionic liquid in the step 4).
9. The method for manufacturing a semi-solid aluminum electrolytic capacitor as claimed in claim 7, wherein: between said steps 3) and 4), the core is immersed in a treatment liquid and dried; the treatment fluid comprises a solvent and a solute, wherein the solvent comprises a water-based high polymer material with a characteristic of difficult volatilization, an organic solvent with a boiling point below 100 ℃, an organic solvent with a boiling point above 150 ℃ and water, and the solute is one or more of an organic acid compound and an inorganic acid compound.
10. The method for manufacturing a semi-solid aluminum electrolytic capacitor as claimed in claim 7, wherein: the conductive high molecular polymer in the step 3) comprises one of polythiophene or a derivative thereof, polypyrrole or a derivative thereof, polyaniline or a derivative thereof.
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