CN112735834B - Novel solid-state aluminum electrolytic capacitor and preparation method thereof - Google Patents

Novel solid-state aluminum electrolytic capacitor and preparation method thereof Download PDF

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CN112735834B
CN112735834B CN202011600249.8A CN202011600249A CN112735834B CN 112735834 B CN112735834 B CN 112735834B CN 202011600249 A CN202011600249 A CN 202011600249A CN 112735834 B CN112735834 B CN 112735834B
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electrolytic capacitor
aluminum electrolytic
cathode foil
carbon fiber
foil
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CN112735834A (en
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胡少强
贾明
张茂贵
刘晓明
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Hunan Aihua Group Co Ltd
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Hunan Aihua Group Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15Solid electrolytic capacitors
    • H01G9/151Solid electrolytic capacitors with wound foil electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/04Electrodes or formation of dielectric layers thereon
    • H01G9/042Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/0425Electrodes or formation of dielectric layers thereon characterised by the material specially adapted for cathode
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/04Electrodes or formation of dielectric layers thereon
    • H01G9/042Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium

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

A novel solid-state aluminum electrolytic capacitor comprises anode foil, electrolytic paper and cathode foil, wherein the anode foil, the electrolytic paper and the cathode foil are wound or folded into a core bag which is packaged in a shell; a solid electrolyte is formed between the anode foil and the cathode foil; the cathode foil comprises carbon fiber yarn, and the surface of the carbon fiber yarn is coated with a composite material of sodium lignosulfonate-doped polypyrrole. Compared with the traditional solid aluminum electrolytic capacitor, the novel solid aluminum electrolytic capacitor is 18 percent higher; the capacitance can also be maintained at 92.3% after 20000 cycles.

Description

Novel solid-state aluminum electrolytic capacitor and preparation method thereof
Technical Field
The invention relates to an aluminum electrolytic capacitor, in particular to a novel solid aluminum electrolytic capacitor and a preparation method thereof.
Background
At present, aluminum foils are used as the anode foil and the cathode foil of the aluminum electrolytic capacitor, wherein a solid electrolyte is formed between the anode foil and the cathode foil of the solid aluminum electrolytic capacitor, and the solid electrolyte is a high molecular conductive polymer, such as PEDOT. In actual development and production, the capacitor for the capacitor focuses on the anode foil, that is, the surface area of the anode foil is increased as much as possible, however, in the medium-high voltage aluminum electrolytic capacitor, because the oxide film on the surface of the anode foil is relatively thick, the surface area of the anode foil is difficult to be effectively increased, otherwise the voltage resistance value of the anode foil is difficult to be ensured. However, little attention has been paid to the surface area of the cathode foil.
With the development of electronic products, the development trend of aluminum electrolytic capacitors is miniaturization and the requirement of mechanical properties is higher and higher. Due to the limitation of the surface areas of the anode foil and the cathode foil and the inherent characteristics of the electrolyte of the solid aluminum electrolytic capacitor, the traditional solid aluminum electrolytic capacitor has the defect that the cycle performance, the capacitor and the mechanical property of the traditional solid aluminum electrolytic capacitor can hardly meet the requirements of the industry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel solid-state aluminum electrolytic capacitor with high capacitance and good cycle performance and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a novel solid-state aluminum electrolytic capacitor comprises anode foil, electrolytic paper and cathode foil, wherein the anode foil, the electrolytic paper and the cathode foil are wound or folded into a core bag which is packaged in a shell; a solid electrolyte is formed between the anode foil and the cathode foil; the cathode foil comprises carbon fiber yarns, and the surfaces of the carbon fiber yarns are coated with a composite material of sodium lignosulfonate-doped polypyrrole.
Preferably, in the novel solid-state aluminum electrolytic capacitor, the weight of the sodium lignosulfonate-doped polypyrrole composite material is 15-40% of the total composite material.
Preferably, the solid electrolyte of the novel solid aluminum electrolytic capacitor includes thiophene and its derivatives, or polyaniline and its derivatives, or polypyrrole and its derivatives.
A preparation method of a novel solid-state aluminum electrolytic capacitor comprises the following steps;
1) preparing a cathode foil;
firstly, cutting carbon fiber yarns into preset sizes;
washing the carbon fiber yarn with acetone, ethanol and deionized water in sequence;
electrochemically polymerizing carbon fiber yarn in working electrolyte for 60-200 min to obtain a fibrous electrode, wherein the carbon fiber yarn is used as a working electrode, and a cylindrical stainless steel net is used as a counter electrode; the working electrolyte comprises pyrrole and HClO4And sodium lignosulfonate; the concentration of pyrrole is 4-8g/L, the concentration of sodium lignosulfonate is 2-4g/L, and HClO4The concentration of (A) is 0.1-0.2 mol/L; the current is 2-4mA during electrochemical reaction. In the present invention, when the electrochemical deposition time exceeds 200 minutes, the composite material of sodium lignosulfonate-doped polypyrrole is deposited on the surface of the carbon fiber yarn too much, one increases the thickness of the cathode foil, and the other reduces the utilization of the active material, thereby reducing the effective specific surface area of the cathode foil.
Fourthly, the fibrous electrode obtained in the third step is washed by deionized water and then dried for more than 10 hours under the protection of inert atmosphere at the temperature of 25-50 ℃ to obtain cathode foil;
2) winding or folding the anode foil, the electrolytic paper and the cathode foil into a core package;
3) impregnating the core package of the step 2) with a solution of a solid electrolyte;
4) drying;
5) and sealing and assembling the core bag in the shell.
In the preparation method of the novel solid aluminum electrolytic capacitor, preferably, in the step 4), after the core package is dried, the core package is immersed in the polyglycerol, and then the core package is hermetically assembled in the shell.
In the preparation method of the novel solid aluminum electrolytic capacitor, preferably, 80-90% of the core package body is immersed in the polyglycerol solution when the core package is impregnated with the polyglycerol.
Compared with the prior art, the invention has the advantages that: compared with the traditional solid aluminum electrolytic capacitor, the novel solid aluminum electrolytic capacitor has the capacitance which is 18 percent higher; the capacitance can also be maintained at 92.3% after 20000 cycles.
Drawings
Fig. 1 is an SEM electron micrograph of the cathode foil prepared in example 1.
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 novel solid-state aluminum electrolytic capacitor comprises anode foil, electrolytic paper and cathode foil, wherein the anode foil, the electrolytic paper and the cathode foil are wound or folded into a core bag which is packaged in a shell; a solid electrolyte is formed between the anode foil and the cathode foil; the cathode foil comprises carbon fiber yarn, and the surface of the carbon fiber yarn is coated with a composite material of sodium lignosulfonate-doped polypyrrole. In the composite material of polypyrrole doped with sodium lignosulfonate, the weight ratio of polypyrrole to sodium lignosulfonate is 5: 2. In this example, the solid electrolyte is PEDOT: PSS. In this embodiment, the weight of the solid electrolyte is much less than the amount of solid electrolyte in a conventional solid aluminum electrolytic capacitor, and in the present invention, PEDOT: the PSS plays a role in conducting electricity between the surface of the anode foil and the cathode foil, so that the internal resistance of the solid-state aluminum electrolytic capacitor is reduced. In the embodiment, the sodium lignosulfonate-doped polypyrrole composite material coated on the surface of the cathode foil actually plays a role of a solid electrolyte; that is, in the present embodiment, the solid electrolyte is actually a composite electrolyte.
The embodiment also provides a preparation method of the novel solid-state aluminum electrolytic capacitor, which comprises the following steps;
1) preparing a cathode foil;
firstly, cutting carbon fiber yarns into preset sizes;
washing the carbon fiber yarn with acetone, ethanol and deionized water in sequence;
electrochemically polymerizing carbon fiber yarn in working electrolyte for 120 minutes to obtain a fibrous electrode, wherein the carbon fiber yarn is used as a working electrode, and a cylindrical stainless steel net is used as a counter electrode; the working electrolyte comprises pyrrole and HClO4And sodium lignosulfonate; the concentration of pyrrole is 5g/L, the concentration of sodium lignosulfonate is 2g/L, and HClO4The concentration of (A) is 0.1 mol/L; the current is 3mA during the electrochemical reaction;
fourthly, the fibrous electrode obtained in the third step is washed by deionized water and then dried for more than 10 hours under the condition of 40 ℃ under the protection of inert atmosphere, and cathode foil is obtained;
2) winding or folding the anode foil, the electrolytic paper and the cathode foil into a core package;
3) impregnating the core package of the step 2) with a solution of a solid electrolyte;
4) drying;
5) and sealing and assembling the core bag in the shell.
In this embodiment, after the core package is dried in step 4), the core package is immersed in the polyglycerol, and then the core package is hermetically assembled in the housing. When the core package is impregnated with the polyglycerol, 80% -90% of the core package body is immersed in the polyglycerol solution.
After the impregnation of the polyglycerol is finished, the outermost layer of the core package is impregnated with a layer of polyglycerol, and the macromolecular characteristic of the polyglycerol can prevent a part of heat from entering the core package when the aluminum electrolytic capacitor is welded on a circuit board. The temperature transferred to the aluminum electrolytic capacitor during welding can reach 200 to 300 ℃; the temperature is transferred to the core package, so that a gap is easily generated between the high-molecular conductive polymer and the anode foil, and under the impact of large current, the gap is expanded to reduce the capacity of the capacitor; under the characteristic of the macromolecule of the polyglycerol, when heat generated by welding is transferred to the core package, the temperature is reduced to more than 100 ℃, so that the core package is protected. Meanwhile, the polyglycerol on the outer layer of the core bag can also transfer the heat inside the core bag to the shell, so that the dispersion of the heat above the core bag is accelerated, and the large-current impact resistance of the capacitor is enhanced.
In the embodiment, after the carbon fiber yarn is subjected to electrochemical deposition, the active material, namely the sodium lignosulfonate-doped polypyrrole composite material coated on the surface of the carbon fiber yarn, has high adhesion with the carbon fiber yarn, and meanwhile, in the charge and discharge cycle of the capacitor, the carbon fiber yarn plays a skeleton role, and the carbon fiber yarn has small expansion and contraction in the charge and discharge cycle of the capacitor, so that the cycle performance and the mechanical stability of the solid-state aluminum electrolytic capacitor are ensured.
The SEM electron scan of the cathode foil prepared in this example is shown in fig. 1 as a cauliflower-like micro-cone with a rough surface, which increases the surface area of the cathode foil, and facilitates PEDOT due to the rough surface of the cathode foil; the penetration of PSS not only increases the effective surface area of the capacitor cathode foil, but also reduces the internal resistance of the capacitor.
In order to compare the performance of the novel solid state capacitor of this example, comparative example 1 was prepared, in which comparative example 1 the cathode foil was a conventional aluminum foil, and the rest was the same as in example 1. The capacitance of the novel solid-state aluminum electrolytic capacitor prepared in the example 1 reaches 25.9 muF, while the capacitance of the solid-state aluminum electrolytic capacitor prepared in the comparative example 1 is only 21.9 muF; the internal resistance of the novel solid aluminum electrolytic capacitor in example 1 was only 39.5 m.OMEGA., whereas the internal resistance in comparative example 1 reached 57.8 m.OMEGA.; after 20000 cycles, the capacitance retention rate of the novel solid aluminum electrolytic capacitor in example 1 reaches 92.3%; and the solid aluminum electrolytic capacitor of comparative example 1 has a capacity retention rate of 85.3% after 20000 cycles. The above data are average data.

Claims (5)

1. A novel solid-state aluminum electrolytic capacitor is characterized in that: the electrolytic cell comprises anode foil, electrolytic paper and cathode foil, wherein the anode foil, the electrolytic paper and the cathode foil are wound or folded into a core package, and the core package is packaged in a shell; a solid electrolyte is formed between the anode foil and the cathode foil; the cathode foil comprises carbon fiber yarns, and the surfaces of the carbon fiber yarns are coated with a composite material of sodium lignosulfonate-doped polypyrrole; the solid electrolyte is PEDOT: PSS.
2. The novel solid-state aluminum electrolytic capacitor of claim 1, characterized in that: in the composite material of the sodium lignosulfonate-doped polypyrrole, the weight of the sodium lignosulfonate accounts for 15-40% of the total composite material.
3. A method for manufacturing a novel solid-state aluminum electrolytic capacitor according to claim 1 or 2, characterized in that: comprises the following steps;
1) preparing a cathode foil;
cutting the carbon fiber yarn into a preset size;
Figure DEST_PATH_IMAGE001
washing the carbon fiber yarn with acetone, ethanol and deionized water in sequence;
Figure DEST_PATH_IMAGE002
carrying out electrochemical polymerization on carbon fiber yarns in working electrolyte for 60-200 minutes to obtain a fibrous electrode, wherein the carbon fiber yarns are used as the working electrode, and a cylindrical stainless steel net is used as a counter electrode; the working electrolyte comprises pyrrole and HClO4And sodium lignosulfonate; the concentration of pyrrole is 4-8g/L, the concentration of sodium lignosulfonate is 2-4g/L, and HClO4The concentration of (b) is 0.1-0.2 mol/L; the current is 2-4mA during electrochemical reaction;
Figure DEST_PATH_IMAGE003
will be described in detail
Figure 158566DEST_PATH_IMAGE002
Washing the obtained fibrous electrode by using deionized water, and then drying the fibrous electrode for more than 10 hours at the temperature of 25-50 ℃ under the protection of inert atmosphere to obtain cathode foil;
2) winding or folding the anode foil, the electrolytic paper and the cathode foil into a core package;
3) impregnating the core package of the step 2) with a solution of a solid electrolyte;
4) drying;
5) and sealing and assembling the core bag in the shell.
4. The method for preparing the novel solid-state aluminum electrolytic capacitor according to claim 3, characterized in that: and 4) drying the core bag, immersing the core bag into polyglycerol, and sealing and assembling the core bag in the shell.
5. The method for preparing the novel solid-state aluminum electrolytic capacitor according to claim 4, wherein the method comprises the following steps: when the core bag is impregnated with the polyglycerol, 80-90% of the core bag body is immersed in the polyglycerol solution.
CN202011600249.8A 2020-12-29 2020-12-29 Novel solid-state aluminum electrolytic capacitor and preparation method thereof Active CN112735834B (en)

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* Cited by examiner, † Cited by third party
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JP3705306B2 (en) * 1996-04-26 2005-10-12 日本ケミコン株式会社 Solid electrolytic capacitor and manufacturing method thereof
CN1220226C (en) * 1997-06-20 2005-09-21 松下电器产业株式会社 Electrolytic condenser and manufacture method thereof
JP4136092B2 (en) * 1998-07-17 2008-08-20 ニチコン株式会社 Polarized aluminum electrolytic capacitor
CN108447696B (en) * 2018-02-05 2019-11-08 三峡大学 A kind of preparation method and applications of polypyrrole/conduction carbon cloth combination electrode
CN109727777A (en) * 2018-12-13 2019-05-07 益阳市万京源电子有限公司 The preparation method of comprehensive high molecular aluminium electrolytic capacitor

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