CN112038095B - Solid-state aluminum electrolytic capacitor based on conductive polyaniline-polyimide film and preparation method thereof - Google Patents
Solid-state aluminum electrolytic capacitor based on conductive polyaniline-polyimide film and preparation method thereof Download PDFInfo
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- CN112038095B CN112038095B CN202011015512.7A CN202011015512A CN112038095B CN 112038095 B CN112038095 B CN 112038095B CN 202011015512 A CN202011015512 A CN 202011015512A CN 112038095 B CN112038095 B CN 112038095B
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- conductive polyaniline
- polyimide
- polyimide film
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
Abstract
A solid-state aluminum electrolytic capacitor based on a conductive polyaniline-polyimide film comprises a core bag and a shell, wherein the core bag is hermetically arranged in the shell through a rubber plug, the core bag is formed by winding an anode foil, electrolytic paper and a cathode foil, and a conductive polyaniline-polyimide film is formed between the anode foil and the cathode foil; the conductive polyaniline accounts for 50-80% of the total weight of the conductive polyaniline-polyimide film. In the invention, the polyimide polymer film is inserted on the poly (aniline) polymer film, the poly (aniline) polymer film and the polyimide polymer film are mutually embedded, and the compatibility of the two polymers has good mechanical property compared with the simple poly (aniline) polymer film, so that the retention rate of the capacitance is improved when the solid-state capacitor is subjected to surge test.
Description
Technical Field
The invention relates to a solid aluminum electrolytic capacitor, in particular to a solid aluminum electrolytic capacitor based on a conductive polyaniline-polyimide film and a preparation method thereof.
Background
The capacitor is one of three basic components in the electronic industry and is widely applied to various electronic products. Liquid electrolytic capacitors are currently predominant in the market, occupying a large share of the capacitor market. However, with the development of electronic science and technology, electronic products are being developed to have higher frequency, smaller size and higher reliability, and the requirements for the performance of capacitors, particularly at high frequency and high and low temperature, are also increasing accordingly.
The liquid electrolytic capacitor has a structure described below: an anode foil and a cathode foil which are formed by the action of valve metals such as aluminum are respectively connected with the outgoing lines, a separation plate is inserted between the anode foil and the cathode foil, then the anode foil and the cathode foil are wound to form a capacitor core package, electrolyte is impregnated into the capacitor core package, then the core package impregnated with the electrolyte is packaged in a shell made of aluminum or other materials, and the shell is sealed.
Since the liquid electrolytic capacitor uses the electrolyte as the electrolyte, the electrolyte of the liquid electrolytic capacitor gradually volatilizes with the lapse of the use time and the increase of the use temperature, so that the capacity thereof is decreased and the impedance is increased. The solid electrolytic capacitor is a novel electrolytic capacitor developed from a liquid electrolytic capacitor, the electrolyte in the liquid electrolytic capacitor is replaced by a high-molecular conductive polymer, the problems which plague the liquid electrolytic capacitor, particularly the problems of short service life, high temperature resistance, poor low-temperature performance and poor stability, and the speed of capacity change of the solid electrolytic capacitor is far less than that of the liquid electrolytic capacitor under the high-temperature environment.
With the development of solid aluminum electrolytic capacitors, there are three main families of electrolytes for solid aluminum electrolytic capacitors, PEDOT, polypyrrole and Polyaniline (PANI), among which polyaniline is representative of patents: 201410319836.8, a solid electrolytic capacitor based on nano-scale graphene composite polyaniline; the electrolyte component in this patent is Polyphenylammonium (PANI). With the development of solid aluminum electrolytic capacitors, it is found that the electrolyte adopts the polyaniline, and the polyaniline has high brittleness, so that the service life of the capacitor is not high, specifically, the capacitor retention rate is poor in performance during surge test.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a solid aluminum electrolytic capacitor based on a conductive polyaniline-polyimide film with long service life 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 based on a conductive polyaniline-polyimide film comprises a core package and a shell, wherein the core package is arranged in the shell in a sealing mode through a rubber plug, the core package is formed by winding an anode foil, electrolytic paper and a cathode foil, and the conductive polyaniline-polyimide film is formed between the anode foil and the cathode foil; the conductive polyaniline accounts for 50-80% of the total weight of the conductive polyaniline-polyimide film.
In the solid aluminum electrolytic capacitor based on the conductive polyaniline-polyimide film, preferably, the conductive polyaniline accounts for 70% of the total weight of the conductive polyaniline-polyimide film.
Preferably, the conductive polyaniline-polyimide film is doped with nano-graphene powder.
A preparation method of a solid-state aluminum electrolytic capacitor based on a conductive polyaniline-polyimide film comprises the following steps:
1) winding the anode foil, the electrolytic paper and the cathode foil into a core package for later use;
2) drying the poly (ammonium benzene) polymer solution in a vacuum oven for at least 12 hours at the temperature of 60-80 ℃ to remove water;
3) dissolving polyimide in an N-methyl pyrrolidone solution, and fully and uniformly stirring, wherein the weight ratio of the polyimide to the N-methyl pyrrolidone is 1:10-1: 4;
4) slowly dissolving the poly (ammonium benzene) polymer solution obtained in the step 2) in the solution obtained in the step 3), and fully and uniformly stirring at the temperature of 60-80 ℃;
5) standing the solution obtained in the step 4) for more than 12 hours;
6) impregnating the core wrap in the solution obtained in the step 5), wherein the impregnation mode comprises vacuum impregnation or inert gas pressurization impregnation;
7) the core package is dried, the dried core package is encased in an aluminum shell, and sealed.
In the above method for preparing the solid-state aluminum electrolytic capacitor based on the conductive polyaniline-polyimide film, preferably, the polyaniline polymer solution in the step 4) is slowly dissolved in the solution in the step 3) and then stirred for at least 48 hours, and ultrasound is turned on while mechanical stirring.
In the above method for preparing a solid aluminum electrolytic capacitor based on a conductive polyaniline-polyimide film, preferably, before step 4), the nano-graphene is added in step 3) while the polyimide is dissolved in the N-methylpyrrolidone solution, and the weight of the nano-graphene is 20% to 60% of the weight of the polyimide. In the invention, because the polyimide film and the polyaniline film are mutually embedded and have certain influence on the conductivity of the solid electrolyte, the problem can be solved by adding the nano-graphene. In the invention, due to mutual dragging of the polyimide polymer film and the poly (ammonium benzene sulfonate) polymer film, compared with a pure poly (ammonium benzene sulfonate) polymer film, the internal nano-scale cavity is enlarged, one is that enough space is provided in the polymer film to contain nano-graphene powder, and meanwhile, the polymer film also has enough space for contraction and expansion in the cyclic discharging and charging processes of the capacitor, so that the polymer film is not easy to generate cracks to a certain extent.
In the invention, the polyimide polymer film is inserted on the poly (aniline) polymer film, the poly (aniline) polymer film and the polyimide polymer film are mutually embedded, and the compatibility of the two polymers has good mechanical property compared with the simple poly (aniline) polymer film, so that the retention rate of the capacitance is improved when the solid-state capacitor is subjected to surge test.
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 based on a conductive polyaniline-polyimide film comprises a core package and a shell, wherein the core package is arranged in the shell in a sealing mode through a rubber plug, the core package is formed by winding an anode foil, electrolytic paper and a cathode foil, and the conductive polyaniline-polyimide film is formed between the anode foil and the cathode foil; the conductive polyaniline accounts for 70% of the total weight of the conductive polyaniline-polyimide film. If the content of the polyaniline is too high, cracks are likely to occur in the conductive polymer film (conductive polyaniline-polyimide film) when the solid-state capacitor is subjected to surge test, so that the capacitance of the solid-state capacitor is lost. However, too high a specific gravity of polyimide affects the conductivity of the conductive polymer. In this example, either carbonized or non-carbonized electrolytic paper was used as the electrolytic paper.
In this embodiment, the conductive polyaniline-polyimide film is doped with nano-scaled graphene powder. The nano-scale doped graphene is mainly used for increasing the conductivity of the conductive polymer; thus, the influence of the polyimide film inserted into the conductive polyaniline film on the conductivity can be effectively counteracted. Overall, the conductivity of the conductive polyaniline-polyimide film is sufficient for a capacitor to meet the electrolyte requirements of a solid state capacitor.
The embodiment also provides a preparation method of the solid-state aluminum electrolytic capacitor based on the conductive polyaniline-polyimide film, which comprises the following steps:
1) winding the anode foil, the electrolytic paper and the cathode foil into a core package for later use;
2) drying the poly (ammonium benzene) polymer solution in a vacuum oven for at least 12 hours at a temperature of 70 ℃ to remove water;
3) dissolving polyimide in an N-methyl pyrrolidone solution, and fully and uniformly stirring, wherein the weight ratio of the polyimide to the N-methyl pyrrolidone is 1: 5;
4) adding nanoscale graphene when the polyimide is dissolved in the N-methyl pyrrolidone solution in the step 3), wherein the weight of the nanoscale graphene is 50% of that of the polyimide.
5) Slowly dissolving the poly (ammonium benzene) polymer solution obtained in the step 2) in the solution obtained in the step 4), stirring for 48 hours at the temperature of 70 ℃, and simultaneously starting ultrasonic stirring; the weight ratio of the polyanilinium polymer added to the polyimide in step 3) to the weight of the polyimide was 4: 1.
6) Standing the solution obtained in the step 5) for more than 12 hours; i.e. the solution is degassed.
7) Impregnating the core wrap in the solution obtained in the step 6), wherein the impregnation mode comprises vacuum impregnation or inert gas pressurization impregnation; the inert gas is generally nitrogen.
8) The core package is dried, the dried core package is encased in an aluminum shell, and sealed.
In this embodiment, the subsequent aging, testing, etc. of the solid-state aluminum electrolytic capacitor is the same as the conventional solid-state aluminum electrolytic capacitor.
In this embodiment, the polyaniline polymer is a small molecule polymer, the polyimide polymer is a large molecule polymer, the polyaniline polymer is inserted into the polyimide polymer in the conductive polymer of this embodiment, and the polyimide polymer connects multiple small molecule polyaniline polymers together in a microstructure, thereby increasing the mechanical properties of the conductive polymer of this embodiment.
In this embodiment, the polyimide polymer film is inserted into the poly (phenylene ammonium) polymer film, and the poly (phenylene ammonium) polymer film and the polyimide polymer film are embedded with each other, so that the compatibility of the two polymers has better mechanical properties than a simple poly (phenylene ammonium) polymer film, which improves the retention rate of the capacitor when the solid-state capacitor is subjected to surge test. When the solid-state aluminum electrolytic capacitor obtained in the embodiment is subjected to surge test, the capacitor can keep 96.1% of the rated capacitance after 5000 times of charging and discharging.
Claims (4)
1. A preparation method of a solid-state aluminum electrolytic capacitor based on a conductive polyaniline-polyimide film is characterized by comprising the following steps:
1) winding the anode foil, the electrolytic paper and the cathode foil into a core package for later use;
2) drying the poly (ammonium benzene) polymer solution in a vacuum oven for at least 12 hours at the temperature of 60-80 ℃ to remove water;
3) dissolving polyimide in an N-methyl pyrrolidone solution, and fully and uniformly stirring, wherein the weight ratio of the polyimide to the N-methyl pyrrolidone is 1:10-1: 4;
4) slowly dissolving the poly (ammonium benzene) polymer solution obtained in the step 2) in the solution obtained in the step 3), and fully and uniformly stirring at the temperature of 60-80 ℃;
5) standing the solution obtained in the step 4) for more than 12 hours;
6) impregnating the core wrap in the solution obtained in the step 5), wherein the impregnation mode comprises vacuum impregnation or inert gas pressurization impregnation;
7) drying the core bag, filling the dried core bag into an aluminum shell, and sealing;
a conductive polyaniline-polyimide film is formed between the anode foil and the cathode foil; the conductive polyaniline accounts for 50-80% of the total weight of the conductive polyaniline-polyimide film.
2. The method for preparing the solid-state aluminum electrolytic capacitor based on the conductive polyaniline-polyimide film as claimed in claim 1, wherein: the conductive polyaniline accounts for 70% of the total weight of the conductive polyaniline-polyimide film.
3. The method for preparing the solid-state aluminum electrolytic capacitor based on the conductive polyaniline-polyimide film as claimed in claim 1, wherein: slowly dissolving the poly (ammonium benzene) polymer solution in the step 4) in the solution in the step 3), stirring for at least 48 hours, and starting ultrasound while mechanically stirring.
4. The method for preparing the solid-state aluminum electrolytic capacitor based on the conductive polyaniline-polyimide film as claimed in claim 1, wherein: adding nanoscale graphene when polyimide is dissolved in an N-methyl pyrrolidone solution in the step 3) before the step 4), wherein the weight of the nanoscale graphene is 20% -60% of that of the polyimide.
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| CN202011015512.7A CN112038095B (en) | 2020-09-24 | 2020-09-24 | Solid-state aluminum electrolytic capacitor based on conductive polyaniline-polyimide film and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321322A (en) * | 1999-09-10 | 2001-11-07 | 松下电器产业株式会社 | Solid electrolytic capacitor and production method thereof and conductive polymer polymerizing oxidizing agent solution |
| CN103131137A (en) * | 2011-11-25 | 2013-06-05 | Nec东金株式会社 | Electroconductive polymer composition, electroconductive polymer material, electroconductive substrate, electrode and solid electrolytic capacitor |
| CN104078243A (en) * | 2014-07-07 | 2014-10-01 | 益阳市万京源电子有限公司 | Solid electrolytic capacitor based on graphene composite polyaniline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20140211370A1 (en) * | 2013-01-25 | 2014-07-31 | Ionova Technologies, Inc. | Electrochemical Cell, Related Material, Process for Production, and Use Thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321322A (en) * | 1999-09-10 | 2001-11-07 | 松下电器产业株式会社 | Solid electrolytic capacitor and production method thereof and conductive polymer polymerizing oxidizing agent solution |
| CN103131137A (en) * | 2011-11-25 | 2013-06-05 | Nec东金株式会社 | Electroconductive polymer composition, electroconductive polymer material, electroconductive substrate, electrode and solid electrolytic capacitor |
| CN104078243A (en) * | 2014-07-07 | 2014-10-01 | 益阳市万京源电子有限公司 | Solid electrolytic capacitor based on graphene composite polyaniline |
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