CN112216513A - Method for forming polymer composite material on capacitor element - Google Patents

Method for forming polymer composite material on capacitor element Download PDF

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Publication number
CN112216513A
CN112216513A CN201910626609.2A CN201910626609A CN112216513A CN 112216513 A CN112216513 A CN 112216513A CN 201910626609 A CN201910626609 A CN 201910626609A CN 112216513 A CN112216513 A CN 112216513A
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reaction solution
polymer composite
capacitor element
composite material
forming
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林杰
张皓普
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Apaq Technology Co Ltd
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Apaq Technology Co Ltd
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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
    • H01G9/0029—Processes of manufacture
    • H01G9/0036—Formation of the solid electrolyte layer
    • 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
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • 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
    • 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

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a method for forming a polymer composite material on a capacitor element, which comprises the following preparation steps: forming a homogeneous reaction solution comprising 3, 4-dioxy vinyl thiophene, emulsifier, polystyrene sulfonic acid or its salt oxidant and solvent. A pretreatment step: standing the homogeneous reaction solution to generate microparticles to form a non-homogeneous reaction solution. Impregnation: the capacitor element is immersed in the heterogeneous reaction solution, so that the heterogeneous reaction solution is coated on the capacitor element to form a reaction layer. A polymerization step: heating the reaction layer to make the 3, 4-dioxy vinyl thiophene and polystyrene sulfonic acid or its salt produce polymerization reaction to form high-molecular composite material, and making the reaction layer form a high-molecular composite layer at least including high-molecular composite material.

Description

Method for forming polymer composite material on capacitor element
Technical Field
The present invention relates to a method for forming a polymer composite material on a capacitor device, and more particularly, to a method for forming a polymer composite material on a capacitor device.
Background
Capacitors have been widely used in consumer appliances, computer boards and their peripherals, power supplies, communication products, and basic components of automobiles, and their main functions include: filtering, bypassing, rectifying, coupling, decoupling, inverting, etc. The capacitor is one of the indispensable components in the electronic product. The capacitor has different types according to different materials and applications, including aluminum electrolytic capacitor, tantalum electrolytic capacitor, multilayer ceramic capacitor, thin film capacitor, etc. In the prior art, the solid electrolytic capacitor has the advantages of small size, large capacitance, excellent frequency characteristics and the like, and can be used for decoupling of a power circuit of a central processing unit. Solid electrolytic capacitors use solid electrolytes instead of liquid electrolytes as cathodes, and conductive polymers have been widely used as cathode materials for solid electrolytic capacitors due to their advantages of high conductivity, easy fabrication process, etc.
The conductive polymer used for the cathode of the solid-state capacitor includes polyaniline (PAni), polypyrrole (PPy), polythiophene (PTh), and other materials and derivatives thereof. Wherein, polydioxyethylene group thiophene: the polystyrene sulfonic acid (PEDOT: PSS) complex has excellent conductivity, and compared to other polymers, such as PAni and PPy, etc., PEDOT: the PSS complex has a low polymerization rate, and thus, polymerization can be performed at normal temperature to reduce the difficulty of preparation. In addition, PEDOT: the PSS composite has better weather resistance and heat resistance compared with other polymers. In addition, PEDOT: the PSS compound also has good dispersibility, low production cost, high transparency, and excellent Processability (Processability). Thus, using PEDOT: the PSS compound is useful as a raw material for forming a conductive polymer layer on a cathode portion of a capacitor, and is useful for improving the electrical effect of the capacitor.
There is still a need in the art to provide a method for forming polymer composite material on a capacitor element to simplify the manufacturing process of the capacitor and improve the overall electrical performance of the capacitor.
Disclosure of Invention
The present invention is directed to a method for forming a polymer composite on a capacitor device, which overcomes the shortcomings of the prior art.
In order to solve the above technical problems, one technical solution of the present invention is to provide a method for forming a polymer composite material on a capacitor element. Which comprises a preparation step, a standing step, an impregnation step and a polymerization step. The preparation method comprises the following steps: forming a homogeneous reaction solution comprising 3, 4-dioxy vinyl thiophene, emulsifier, polystyrene sulfonic acid or its salt oxidant and solvent. The standing step comprises the following steps: standing the homogeneous reaction solution to generate microparticles to form a non-homogeneous reaction solution. The impregnation step comprises: the capacitor element is immersed in the heterogeneous reaction solution to coat the heterogeneous reaction solution on the capacitor element to form a reaction layer. The polymerization step comprises: heating the reaction layer to make the 3, 4-dioxy vinyl thiophene and polystyrene sulfonic acid or its salt produce polymerization reaction to form a high molecular composite material, and making the reaction layer form a high molecular composite layer at least including the high molecular composite material.
Further, the microparticles have an average particle diameter of 300 nm to 500 nm, and the standard deviation of the particle diameter of the microparticles is 50 nm to 100 nm.
Still further, the method of forming a polymer composite on a capacitor element, after the step of leaving to stand, comprises: a pretreatment step comprising: purifying the heterogeneous reaction solution.
Further, the non-homogeneous reaction solution is purified by at least one of ion exchange, centrifugation, dialysis, column chromatography, ultrafiltration, or precipitation.
Further, the pretreatment step further comprises: and carrying out homogeneous dispersion on the purified heterogeneous reaction solution, wherein the particle size of microparticles in the heterogeneous reaction solution is 25-100 nanometers, and the standard deviation of the particle size of the microparticles is 30-60 nanometers.
Further, the pretreatment step further comprises: and adding a conductive aid into the purified heterogeneous reaction solution.
Further, the conductive auxiliary agent includes at least one of alcohols, polyalcohols, polyglycerin types, saccharides, high-boiling-point solvents, or alcohol solvents.
Still further, in the preparing step, further comprising: dissolving 3, 4-dioxy ethylene thiophene and the emulsifier in the solvent to form a homogeneous solution; mixing a polystyrene sulfonic acid aqueous solution containing polystyrene sulfonic acid or salts thereof with the homogeneous solution to form a precursor solution; and adding the oxidant into the precursor solution to form the homogeneous reaction solution.
Still further, the polymerizing step further comprises: allowing the reaction layer to form the polymer composite layer at a temperature of 70 ℃ to 90 ℃.
Further, after the polymerizing step, repeating the impregnating step and the polymerizing step at least once.
Still further, the method for forming a polymer composite on a capacitor element further comprises, after the polymerizing step: a drying step, comprising: removing the solvent in the polymer composite layer at a temperature of 180 ℃ to 220 ℃.
One of the advantages of the present invention is that the method for forming a polymer composite material on a capacitor element provided by the present invention can improve the electrical performance of the capacitor by the technical characteristics of "forming a non-homogeneous reaction liquid with microparticles in a standing step" and "immersing the capacitor element in the non-homogeneous reaction liquid in an impregnation step", and can have low Equivalent Series Resistance (ESR) and Leakage Current (LC).
For a better understanding of the features and technical content of the present invention, reference should be made to the following detailed description of the invention and accompanying drawings, which are provided for purposes of illustration and description only and are not intended to limit the invention.
Drawings
Fig. 1 is a schematic side sectional view of a capacitor applied to a polymer composite material formed according to an embodiment of the invention.
Fig. 2 is a schematic structural diagram of a capacitor package structure according to an embodiment of the invention.
Fig. 3 is a schematic perspective view of another capacitor applied to the polymer composite material formed in the embodiment of the invention.
Fig. 4 is a schematic side view of another capacitor package structure according to an embodiment of the invention.
Fig. 5 is a flowchart of a method for forming a polymer composite on a capacitor device according to an embodiment of the present invention.
Detailed Description
The following is a description of the embodiments of the present disclosure relating to a method for forming a polymer composite on a capacitor element, by way of specific examples, and those skilled in the art will understand the advantages and effects of the present disclosure from the disclosure of the present disclosure. The invention is capable of other and different embodiments and its several details are capable of modification and various other changes, which can be made in various details within the specification and without departing from the spirit and scope of the invention. The drawings of the present invention are for illustrative purposes only and are not intended to be drawn to scale. The following embodiments will further explain the related art of the present invention in detail, but the disclosure is not intended to limit the scope of the present invention.
It should be understood that although the terms "first," "second," "third," etc. may be used herein to describe various components, these components should not be limited by these terms. These terms are used primarily to distinguish one element from another. In addition, the term "or" as used herein should be taken to include any one or combination of more of the associated listed items as the case may be.
First, please refer to fig. 1 and fig. 2. Fig. 1 is a schematic side sectional view of a capacitor applied to a polymer composite material according to an embodiment of the present invention. Specifically, the polymer composite material produced by the production method of the present invention can be applied to the conductive polymer layer 102 of the cathode portion N of the capacitor 1. Fig. 2 is a schematic structural diagram of a capacitor package structure according to an embodiment of the present invention. A stacked solid electrolytic capacitor package structure, the capacitor 1 in fig. 1, and the capacitor unit 42 in the stacked solid electrolytic capacitor package structure 4 in fig. 2 are shown in fig. 2.
For example, as shown in fig. 1, the capacitor 1 may include a valve metal foil 100, an oxide layer 101 covering the valve metal foil 100, a conductive polymer layer 102 covering a portion of the oxide layer 101, a carbon glue layer 103 covering the conductive polymer layer 102, and a silver glue layer 104 covering the carbon glue layer 103. The structure of the capacitor 1 can be adjusted according to the actual requirements of the product. The conductive polymer layer 102 mainly serves as a solid electrolyte of the capacitor 1.
Specifically, the conductive polymer layer 102 may be formed by the method of forming a polymer composite on a capacitor device according to the present invention. Accordingly, the capacitor element in the present invention may include the valve metal foil 100 shown in fig. 1 and the oxide layer 101 thereon.
As shown in fig. 2, the stacked solid electrolytic capacitor 4 includes a plurality of capacitor cells 42 stacked in sequence. In addition, the stacked type solid electrolytic capacitor 4 includes a conductive holder 41. The conductive holder 41 includes a first conductive terminal 411 and a second conductive terminal 412 separated from the first conductive terminal 411 by a predetermined distance. In addition, the plurality of capacitor units 42 stacked in sequence and electrically connected to each other have a first positive electrode portion P1 electrically connected to the first conductive terminal 411 of the corresponding conductive holder 41 and a first negative electrode portion N1 electrically connected to the second conductive terminal 412 of the corresponding conductive holder 41. In addition, a plurality of capacitor units 42 stacked in sequence and electrically connected to each other may be encapsulated by the encapsulant 43, thereby forming the stacked solid electrolytic capacitor 4.
Please refer to fig. 3 and fig. 4. Fig. 3 is a schematic perspective view of another capacitor applied to the polymer composite according to the embodiment of the present invention, and fig. 4 is a schematic side view of another capacitor package structure according to the embodiment of the present invention. Shown in fig. 4 is a package structure of a wound type solid electrolytic capacitor.
As shown in fig. 4, the winding-type solid electrolytic capacitor package structure 3 includes: a roll-to-roll assembly 31, a package assembly 32, and a conductive assembly 33. Referring to fig. 3, the rolled assembly 31 includes a rolled positive conductive foil 311, a rolled negative conductive foil 312, and two rolled separator foils 313. Further, one of the two rolled separator foils 313 is disposed between the rolled positive conductive foil 311 and the rolled negative conductive foil 312, and one of the rolled positive conductive foil 311 and the rolled negative conductive foil 312 is disposed between the two rolled separator foils 313. The wound release foil 313 may be release paper or paper foil to which the polymer composite material provided by the present invention is attached by the manufacturing method provided by the present invention. However, the present invention is not limited thereto. In another embodiment of the present invention, in the method for forming a polymer composite material on a capacitor device provided by the present invention, the polymer composite material may be formed on at least one of the wound positive electrode conductive foil 311, the wound negative electrode conductive foil 312, and the two wound separation foils 313.
Further, referring to fig. 4, the winding assembly 31 is wrapped inside the packaging assembly 32. For example, the package assembly 32 includes a capacitor casing structure 321 (e.g., an aluminum shell or other metal casing) and a bottom end sealing structure 322, the capacitor casing structure 321 has an accommodating space 3210 for accommodating the roll-up component 31, and the bottom end sealing structure 322 is disposed at the bottom end of the capacitor casing structure 321 to seal the accommodating space 3210. In addition, the package assembly 32 may be a package body made of any insulating material.
The conductive element 33 includes a first conductive pin 331 electrically contacting the wound positive conductive foil 311 and a second conductive pin 332 electrically contacting the wound negative conductive foil 312. For example, the first conductive pin 331 has a first embedded portion 3311 covered inside the package assembly 32 and a first exposed portion 3312 exposed outside the package assembly 32, and the second conductive pin 332 has a second embedded portion 3321 covered inside the package assembly 32 and a second exposed portion 3322 exposed outside the package assembly 32.
Next, a method for forming a polymer composite material on a capacitor element according to the present invention will be described. Please refer to fig. 5. Fig. 5 is a flowchart of a method for forming a polymer composite on a capacitor device according to an embodiment of the present invention. The method provided by the invention comprises a preparation step (step S100), a standing step (step S120), a pretreatment step (step S140), an impregnation step (step S160), a polymerization step (step S180) and a drying step (step S200) which are sequentially carried out.
First, in the preparation step, 3,4-Ethylenedioxythiophene (EDOT), an oxidizing agent and polystyrene sulfonic acid or its salt are added to water (solvent) to form a homogeneous reaction solution. The homogeneous reaction solution is a precursor solution for forming the polymer composite material. After chemical reaction occurs among all components in the homogeneous reaction liquid, the polymer composite material can be formed. Specifically, the polymerization reaction between 3, 4-dioxyvinyl thiophene and polystyrenesulfonic acid or salts thereof contained in the homogeneous reaction solution starts to proceed in the presence of an oxidizing agent to form polydioxyethylene thiophene: polystyrene sulfonic acid (PEDOT: PSS) complex.
In this embodiment, the oxidizing agent may be a persulfate, for example: ammonium persulfate, sodium persulfate, potassium persulfate, or combinations thereof. Polystyrene sulfonic acid or its salts may be, but are not limited to: polystyrene sulfonic acid, ammonium polystyrene sulfonate, sodium polystyrene sulfonate, or combinations thereof. And the homogeneous reaction liquid comprises 0.16 to 0.68 weight percent of 3, 4-dioxyethylene thiophene, 0.26 to 1.11 weight percent of oxidant and 0.5 to 2 weight percent of polystyrene sulfonic acid or salts thereof, wherein the total weight of the homogeneous reaction liquid is 100 weight percent.
In fact, in the conventional method for producing a polymer composite material, iron salt is often used as an oxidizing agent. However, the electric performance of the capacitor containing the polymer composite material can be greatly improved by using persulfate as an oxidant and using polystyrene sulfonic acid or salts thereof as a reactant of polymerization reaction. For example, compared to the prior art that employs iron salt as the oxidant and p-toluenesulfonic acid as the reactant of the polymerization reaction, the present application employs persulfate as the oxidant and polystyrenesulfonic acid or its salt as the reactant of the polymerization reaction, so as to improve the leakage current of the capacitor (e.g., 25V capacitor).
In addition to this, the mixed solution may further include other additives such as: an emulsifier. The emulsifier may include a nonionic surfactant, a cationic surfactant, and an anionic surfactant. For example, the non-ionic surfactant may be TritonTM、
Figure BDA0002127314040000061
DynalTM、NonidetTMPolyethylene glycol Sorbitan alkyl esters (polyoxyethyleneglycol Sorbitan alkyl esters), ethoxylated hydrogenated Castor oil (Castor oil ethoxylates), polypropylene glycol fatty acid esters (Propylene glycol esters of fatty acids), Polyoxyethylene glycerol fatty acid esters (polyoxyethyleneglycol esters of fatty acids), Sorbitan fatty acid esters (Sorbitane esters of fatty acids), Polyoxyethylene phytosterols (polyoxyethyleneglycol esters) or combinations thereof. The cationic surfactant can be cetyl trimethylammonium bromide, behenyl trimethylammonium chloride, octadecyl trimethylammonium chloride, alkyl dimethylbenzyl ammonium chloride, or combinations thereof. The anionic surfactant may be sodium lauryl sulfate, polyoxyethylene lauryl ether glycolate (Glycolic acid lauryl ether), 4-nonylphenyl ether glycolate (Glycolic acid ethoxylate-4-nonylphenyl ether), Potassium lauryl phosphate (Potassium monolaurate), Disodium laureth sulfosuccinate (sodium laureth sulfosuccinate), sodium laureth sulfate, sodium dodecylbenzenesulfonate or a combination thereof.
In embodiments of the present invention, the solvent may also be an alcohol. However, it is worth noting that the use of water as a solvent can reduce the cost, meet the environmental requirements, and effectively overcome the problem that the solid state capacitor is short-circuited under high voltage. In addition, compared to the existing PEDOT: compared with the PSS dispersion liquid, the mixed solution adopting water as a solvent has no problem related to the storage life.
In the preparing step (step S100), the following steps may be further included: dissolving 3, 4-dioxy ethylene thiophene and an emulsifier in water to form a homogeneous solution; mixing a polystyrene sulfonic acid aqueous solution containing polystyrene sulfonic acid or salts thereof with a homogeneous solution to form a precursor solution; and adding an oxidant to the precursor solution to form a homogeneous reaction solution. In addition, the step of dissolving 3, 4-dioxyvinyl thiophene with an emulsifier in water may include stirring at room temperature for 1.5 to 2.5 hours.
In the step of standing (step S120), the following steps may be further included: standing the homogeneous reaction solution to generate microparticles, and microscopically forming a non-homogeneous reaction solution. Specifically, the standing step may be to allow the homogeneous reaction solution to stand at a temperature of 10 ℃ to 30 ℃ for 2 hours to 24 hours to form a heterogeneous reaction solution. In addition, the average particle diameter of the microparticles in the heterogeneous reaction solution is 300 nm to 500 nm, and the standard deviation of the particle diameter of the microparticles is 50 nm to 100 nm.
In the standing step (step S120), the 3, 4-dioxyvinyl thiophene tends to pre-polymerize and agglomerate to form poly (dioxyvinyl thiophene), and the polystyrenesulfonic acid or its salt adheres to the poly (dioxyvinyl thiophene). That is, microscopically, the structure of the microparticles consists essentially of a core formed of polydioxyethylene thiophene, and polystyrene sulfonic acid attached to an outer layer of polydioxyethylene thiophene.
In addition, the microparticles in the heterogeneous reaction solution can reduce the hydrophobic interaction between the heterogeneous reaction solution and the capacitor element, that is, can increase the effect of immersing the capacitor element in the heterogeneous reaction solution. Therefore, the capacitance of the capacitor can be further improved, the equivalent series resistance of the capacitor can be reduced, and the risks of leakage current and short circuit can be reduced.
Next, in the preprocessing step (step S140), the preprocessing step may further include: purifying the heterogeneous reaction solution (step S141); adding a conductive aid to the heterogeneous reaction solution (step S142); and homogeneously dispersing the heterogeneous reaction solution (step S143).
In step S141, the purification method may be, but is not limited to: at least one of ion exchange, centrifugation, dialysis, column chromatography, ultrafiltration, and precipitation. In this example, the heterogeneous reaction solution was purified by an ion exchange method. Specifically, 1 kg of the heterogeneous reaction solution is mixed with 60 g to 100 g of a strongly acidic ion exchange resin at room temperature and stirred for 6 hours, whereby cations in the heterogeneous reaction solution can be exchanged. Then, 1 kg of the heterogeneous reaction solution is mixed with 70 g to 120 g of a weakly basic ion exchange resin and stirred for 6 hours to exchange strongly acidic anions in the heterogeneous reaction solution, for example: SO (SO)4 2-，Cl-Or NO3-。
In step S142, the conductive aid may include: polyols, polyglycols, sugars, high boiling point solvents or alcoholic solvents. Among the polyols, may be, but are not limited to: ethylene glycol, glycerol or diethylene glycol. Polyols may be, but are not limited to: polypropylene glycol or polyethylene glycol with molecular weight of 200, 300, 400, 600, 1000, 1500, 2000. The saccharide may be, but is not limited to: sorbitol (Sorbitol), Xylitol (Xylitol), Maltitol (Maltitol), Meso-erythritol (Meso-erythritol), Glucose (Glucose), Lactose (Lactose) or Fructose (frutotose). High boiling point solvents such as but not limited to: dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), gamma-butyrolactone (gamma-GBL), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), Sulfolane (Sulfolane), Caprolactam (caprolam), 1-octyl-2-pyrrolidone (1-octyl-2-pyrrolidone), Propylene carbonate (Propylene carbonate), Ethylene carbonate (Ethylene carbonate), Diethyl carbonate (Diethyl carbonate), or Acetonitrile (Acetonitrile). Also, the above-mentioned various kinds of conductive aids may be blended with each other.
In step S143, the heterogeneous reaction solution may be homogenized using a homogenizer, an ultrasonic pulverizer, or a high-pressure homogenizer. In this example, the heterogeneous reaction solution was homogenized by a high-pressure homogenizer, and the homogenization was repeated five times or more at a pressure of 1500 bar. After homogenization, the average particle diameter of microparticles in the heterogeneous reaction solution is 25 to 100 nm, and the standard deviation of the particle diameter of the microparticles is 30 to 60 nm.
It should be noted that there is no sequential division between step S142 and step S143. That is, after the heterogeneous reaction solution is purified (step S141), the conductive auxiliary is added to the heterogeneous reaction solution (step S142), and the heterogeneous reaction solution is then homogeneously dispersed (step S143). Alternatively, the heterogeneous reaction solution may be first homogeneously dispersed (step S143), and then the conductive assistant may be added to the heterogeneous reaction solution (step S142).
In the impregnation step (step S160), the capacitor element is impregnated in the heterogeneous reaction liquid for 3 to 5 minutes. Then, the capacitor element is further impregnated with the heterogeneous reaction solution under a vacuum condition of 0mmHg to 200mmHg, so that the heterogeneous reaction solution is applied on the capacitor element to form a reaction layer. Specifically, the present invention is to dispose the reactants (i.e., 3, 4-dioxyvinyl thiophene and polystyrene sulfonic acid or its salt in the heterogeneous reaction solution) and microparticles which are not polymerized on the capacitor element. In the impregnation step, the heterogeneous reaction liquid is coated on the surface of the capacitor element and penetrates into the porous structure (e.g., pores) of the capacitor element.
Specifically, the non-homogeneous reaction liquid may be provided on the capacitor element by immersing the capacitor element in a container carrying the non-homogeneous reaction liquid. In order to facilitate the non-homogeneous reaction liquid to be coated on the capacitor element or to facilitate the non-homogeneous reaction liquid to permeate into the pores of the capacitor element. In the impregnation step, ultrasonic waves or vibration may be further used to assist the formation of the reaction layer.
In the polymerization step (step S180), the reaction layer is baked at 70 ℃ to 90 ℃ for 30 minutes to polymerize the reactants (3, 4-dioxyvinyl thiophene and polystyrene sulfonic acid or salts thereof) that are not polymerized in the heterogeneous reaction solution, and the reactants and the microparticles form a polymer composite layer at least comprising the polymer composite material. In particular, the present invention is an in situ polymerization process for forming polymeric composites.
Specifically, in the polymerization step, 3, 4-dioxyvinyl thiophene in the reaction layer and polystyrene sulfonic acid or a salt thereof are subjected to polymerization reaction in the presence of an oxidizing agent to form PEDOT: (ii) a PSS complex. In the invention, the polymer composite material is PEDOT: (ii) a PSS complex.
In addition, the capacitor element may have multiple layers of the high molecular composite thereon. That is, the polymer composite material can be sequentially stacked on the capacitor element by repeating the impregnation step (step S160) and the polymerization step (step S180) to obtain a polymer composite layer with desired thickness and properties.
Finally, in the drying step (step S200), the polymer composite layer is heated to bake the polymer composite layer at a temperature of 180 ℃ to 220 ℃ for 30 minutes to remove the solvent in the polymer composite layer. In a preferred embodiment, the polymer composite layer is dried at a temperature of 200 ℃.
In order to confirm the effect of the method for forming a polymer composite on a capacitor element according to the present invention, examples and test results will be described in detail below. Examples 1 to 3 are examples of preparing a heterogeneous reaction liquid, and examples 4a to 4c and examples 5a to 5c are examples of forming a polymer composite layer on a capacitor element.
[ example 1]
To 996.54 g of water were added 0.68 g of 3, 4-dioxyvinylthiophene, 2 g of sodium polystyrenesulfonate, 0.78 g of ammonium persulfate, and 10 g of cetyltrimethylammonium bromide to prepare a homogeneous reaction solution (step S100). The homogeneous reaction solution was allowed to stand at room temperature for 14 hours to form a heterogeneous reaction solution (step S120). Subsequently, 70 g of a strongly acidic cation exchange resin and 130 g of a weakly basic anion exchange resin were added to the heterogeneous reaction solution, and the mixture was stirred for 6 hours, followed by removal of the ion exchange resin by filtration (step S141). After the filtration, 60 g of polyethylene glycol 300(PEG 300) and 60 g of ethylene glycol were added as the conduction aid, and the conduction aid was uniformly mixed in the heterogeneous reaction solution (step S142). The heterogeneous reaction solution was homogenized under high pressure five times at a pressure of 1500bar (step S143).
[ example 2]
996.54 g of water were added 0.68 g of 3, 4-dioxyvinylthiophene, 2 g of sodium polystyrene sulfonate, 0.78 g of ammonium persulfate and 10 g of DynalTM604, to prepare a homogeneous reaction solution (step S100). The homogeneous reaction solution was allowed to stand at room temperature for 14 hours to form a heterogeneous reaction solution (step S120). Subsequently, 70 g of a strongly acidic cation exchange resin and 130 g of a weakly basic anion exchange resin were added to the heterogeneous reaction solution, and the mixture was stirred for 6 hours to remove the ion exchange resin by filtration (step S141). After the filtration, 100 g of dimethyl sulfoxide and 50 g of sorbitol were added as a conductive aid, and the conductive aid was uniformly mixed in the heterogeneous reaction liquid (step S142). The heterogeneous reaction solution was homogenized under high pressure five times at a pressure of 1500bar (step S143).
[ example 3]
To 987.44 g of water were added 0.68 g of 3, 4-dioxyvinylthiophene, 11.1 g of an 18 weight percent aqueous solution of polystyrenesulfonic acid, 0.78 g of ammonium persulfate, and 10 g of sodium dodecylbenzenesulfonate to prepare a homogeneous reaction solution (step S100). The homogeneous reaction solution was allowed to stand at room temperature for 14 hours to form a heterogeneous reaction solution (step S120). Subsequently, 70 g of a strongly acidic cation exchange resin and 130 g of a weakly basic anion exchange resin were added to the heterogeneous reaction solution, and the mixture was stirred for 6 hours to remove the ion exchange resin by filtration (step S141). After the filtration, 100 g of γ -butyrolactone, 30 g of polyethylene glycol 200, and 20 g of maltitol were added as the conduction aid, and the conduction aid was uniformly mixed in the heterogeneous reaction liquid (step S142). The heterogeneous reaction solution was homogenized under high pressure five times at a pressure of 1500bar (step S143).
Examples 4a to 4c
In examples 4a to 4c, the capacitor element was immersed in the homogeneous reaction solution prepared in examples 1 to 3 for 3 minutes (step S160), and after the immersion, the capacitor element was polymerized at 80 ℃ for 30 minutes (step S180). And further baked at a temperature of 200 ℃ for 30 minutes (step S200). After the capacitor element is cooled to room temperature, electrical measurements are performed, and the detailed electrical measurements are shown in table 1 below.
Examples 5a to 5c
In examples 5a to 5c, the capacitor element was immersed in the homogeneous reaction solution prepared in examples 1 to 3 for 3 minutes (step S160), and after the immersion, the capacitor element was polymerized at 80 ℃ for 30 minutes (step S180), and the immersion and polymerization steps were repeated twice. Finally, baking is performed at a temperature of 200 ℃ for 30 minutes (step S200). After the capacitor element is cooled to room temperature, electrical measurements are performed, and the detailed electrical measurements are shown in table 1 below.
Table 1: electrical property test of capacitor elements in examples 4a to 4c and examples 5a to 5 c.
Figure BDA0002127314040000111
[ advantageous effects of the embodiments ]
One of the advantages of the present invention is that the method for forming a polymer composite material on a capacitor element provided by the present invention can improve the electrical performance of the capacitor by the technical features of "forming a non-homogeneous reaction solution with microparticles in a standing step" and "immersing the capacitor element in the non-homogeneous reaction solution in an impregnation step", thereby having lower equivalent series resistance and leakage current.
Furthermore, by controlling the technical characteristics of "average particle size of microparticles" and "standard deviation of particle size of microparticles", the crystallinity of the polymer composite material can be improved, and the effect of improving the electrical characteristics can be achieved.
Furthermore, by the technical characteristics of purifying the heterogeneous reaction solution, the impurity amount in the formed polymer composite material can be reduced, and the quality of the polymer composite material is improved.
Further, the technical feature of "homogeneously dispersing the heterogeneous reaction liquid" contributes to the formation of a uniform and high-quality conductive polymer layer on the capacitor element.
Furthermore, the technical feature of repeating the impregnation step and the polymerization step at least once is helpful for increasing the capacitance of the capacitor element and reducing the equivalent series resistance.
The disclosure is only a preferred embodiment of the invention, and is not intended to limit the scope of the claims, so that all technical equivalents and modifications using the contents of the specification and drawings are included in the scope of the claims.

Claims (11)

1. A method of forming a polymer composite on a capacitor element, the method comprising:
a preparation step comprising: forming a homogeneous reaction solution comprising 3, 4-dioxy vinyl thiophene, emulsifier, polystyrene sulfonic acid or its salt, oxidant and solvent;
a resting step comprising: standing the homogeneous reaction solution to generate microparticles to form a non-homogeneous reaction solution;
an impregnation step, comprising: immersing the capacitor element in the heterogeneous reaction solution to coat the heterogeneous reaction solution on the capacitor element to form a reaction layer; and
a polymerization step comprising: and heating the reaction layer to enable the 3, 4-dioxy vinyl thiophene and the polystyrene sulfonic acid or the salt thereof to generate polymerization reaction to form the polymer composite material, so that the reaction layer forms a polymer composite layer at least comprising the polymer composite material.
2. The method of claim 1, wherein the average particle diameter of the microparticles is 300 nm to 500 nm, and the standard deviation of the particle diameter of the microparticles is 50 nm to 100 nm.
3. The method for forming a polymer composite material on a capacitor element according to claim 1, wherein the method for forming a polymer composite material on a capacitor element comprises, after the leaving step:
a pretreatment step comprising: purifying the heterogeneous reaction solution.
4. The method of claim 3, wherein the heterogeneous reaction solution is purified by at least one of ion exchange, centrifugation, dialysis, column chromatography, ultrafiltration, or precipitation.
5. The method of claim 3, wherein the preprocessing step further comprises: and carrying out homogeneous dispersion on the purified heterogeneous reaction solution, wherein the particle size of microparticles in the heterogeneous reaction solution is 25-100 nanometers, and the standard deviation of the particle size of the microparticles is 30-60 nanometers.
6. The method of claim 3, wherein the preprocessing step further comprises: and adding a conductive aid into the purified heterogeneous reaction solution.
7. The method of claim 6, wherein the conductive additive comprises at least one of alcohols, polyalcohols, polyglycerols, saccharides, high boiling point solvents, or alcoholic solvents.
8. The method for forming a polymer composite material on a capacitor element according to claim 1, further comprising, in the preparing step:
dissolving 3, 4-dioxy ethylene thiophene and the emulsifier in the solvent to form a homogeneous solution;
mixing a polystyrene sulfonic acid aqueous solution containing polystyrene sulfonic acid or salts thereof with the homogeneous solution to form a precursor solution; and
adding the oxidant into the precursor solution to form the homogeneous reaction solution.
9. The method of forming a polymer composite on a capacitor element according to claim 1, wherein the polymerizing step further comprises: allowing the reaction layer to form the polymer composite layer at a temperature of 70 ℃ to 90 ℃.
10. The method of claim 1, wherein the impregnating step and the polymerizing step are repeated at least once after the polymerizing step.
11. The method of claim 1, wherein the method of forming a polymer composite on a capacitor element further comprises, after the polymerizing step:
a drying step, comprising: removing the solvent in the polymer composite layer at a temperature of 180 ℃ to 220 ℃.
CN201910626609.2A 2019-07-11 2019-07-11 Method for forming polymer composite material on capacitor element Pending CN112216513A (en)

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