CN114927348A - Solid-state aluminum electrolytic capacitor with good stability and preparation method thereof - Google Patents

Solid-state aluminum electrolytic capacitor with good stability and preparation method thereof Download PDF

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Publication number
CN114927348A
CN114927348A CN202210498069.6A CN202210498069A CN114927348A CN 114927348 A CN114927348 A CN 114927348A CN 202210498069 A CN202210498069 A CN 202210498069A CN 114927348 A CN114927348 A CN 114927348A
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pedot
pss
perylene
electrolytic capacitor
aluminum electrolytic
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CN114927348B (en
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赵新国
张超
刘尧虎
潘振炎
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Hunan City University
Hunan Aihua Group Co Ltd
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Hunan City University
Hunan Aihua Group Co Ltd
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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
    • H01G9/02—Diaphragms; Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G13/003—Apparatus or processes for encapsulating capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 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
    • H01G9/0029—Processes of manufacture
    • 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
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

A solid-state aluminum electrolytic capacitor with good stability comprises a shell and a core package, wherein the core package is arranged in the shell in a sealing mode through a rubber plug, the core package comprises an anode foil, electrolytic paper and a cathode foil, a conductive high polymer is formed between the anode foil and the cathode foil, and the conductive high polymer comprises perylene diimide or PEDOT doped with perylene diimide, namely a PSS film. According to the solid aluminum electrolytic capacitor and the preparation method thereof, the PEDOT and PSS high polymer is doped by the perylene bisimide or the perylene bisimide, so that the conductivity of the doped PEDOT and PSS film formed in the core package is high, and meanwhile, the perylene bisimide or the perylene bisimide can prevent the oxidation of the PEDOT and PSS film by oxygen to a certain extent, so that the stability of the solid aluminum electrolytic capacitor is improved.

Description

Solid-state aluminum electrolytic capacitor with good stability and preparation method thereof
Technical Field
The invention relates to a solid-state aluminum electrolytic capacitor, in particular to a solid-state aluminum electrolytic capacitor with good stability and a preparation method thereof.
Background
At present, conductive high polymer in a core bag of the solid aluminum electrolytic capacitor is mainly a PEDOT film or a PEDOT PSS film, wherein when the PEDOT film is formed on the core bag, an oxide film on the surface of an anode foil is damaged; therefore, most manufacturers of solid aluminum electrolytic capacitors adopt the method that PEDOT and PSS films are obtained on core packages after PSS dispersion liquid is dried and directly impregnated into the PEDOT; however, the conductivity of the PEDOT PSS is low, and meanwhile, the PEDOT PSS dispersion liquid, the core package and the core package with the PEDOT PSS film are inevitably contacted with moisture in the air during the production process. After the core bag contains water vapor, the reaction of electrolytic water can occur in the charge and discharge cycle process of the solid aluminum electrolytic capacitor, so that oxygen is generated, and the oxygen can oxidize PEDOT/PSS so as to peel a PEDOT/PSS film from an anode foil, so that the capacitance is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a solid-state aluminum electrolytic capacitor with good stability and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the solid-state aluminum electrolytic capacitor with good stability comprises a shell and a core package, wherein the core package is arranged in the shell in a sealing mode through a rubber plug, the core package comprises an anode foil, electrolytic paper and a cathode foil, a conductive high polymer is formed between the anode foil and the cathode foil, and the conductive high polymer comprises perylene imide or perylene diimide doped PEDOT (polyphenylene sulfide) film.
Preferably, the perylene imide or perylene diimide accounts for 3% -10% of the weight of the PEDOT and the PSS.
In the solid aluminum electrolytic capacitor with good stability, preferably, the core package is impregnated with the dispersion liquid of the conductive high molecular polymer for multiple times, and the dispersion liquid of the conductive high molecular polymer impregnated by the core package for the first time is PEDOT (PSS) dispersion liquid; and the dispersion liquid of the conductive high molecular polymer impregnated for the (N + 1) th time is perylene bisimide or PEDOT doped with perylene bisimide, namely PSS dispersion liquid, wherein N is more than or equal to 1 and less than 4.
A preparation method of a solid-state aluminum electrolytic capacitor with good stability comprises the following steps:
1) uniformly dispersing perylene bisimide or perylene bisimide in a solvent;
2) adding PEDOT and PSS into the dispersion liquid in the step 1), wherein the weight concentration of the PEDOT and PSS in the dispersion liquid is not more than 8%; the weight of the perylene diimide or the perylene diimide is 3 to 10 percent of that of PEDOT (PSS);
3) the core bag is impregnated with the dispersion liquid in the step 2), and a conductive high molecular polymer film is formed in the core bag after drying;
4) the core package is sealed in the shell through the rubber plug to form the solid aluminum electrolytic capacitor.
In the preparation method of the solid aluminum electrolytic capacitor with good stability, preferably, the core package is impregnated with the dispersion liquid obtained in step 2) for multiple times.
Preferably, in the preparation method of the solid aluminum electrolytic capacitor with good stability, before the step 3), the core package is impregnated with the PEDOT: PSS dispersion liquid, and the core package is dried to form a PEDOT: PSS film.
In the preparation method of the solid aluminum electrolytic capacitor with good stability, preferably, the solvent includes one or more of DMSO, ethylene glycol, glycerol, NMP, resin, PVDF, xylene, and methanol.
In the preparation method of the solid aluminum electrolytic capacitor with good stability, preferably, the perylene diimide or perylene diimide in the step 1) is purified before being added into the solvent, and the purification step includes
Figure 100002_DEST_PATH_IMAGE002
Dissolving perylene bisimide or perylene bisimide powder in concentrated sulfuric acid under ultrasonic stirring;
Figure 100002_DEST_PATH_IMAGE004
at the step of
Figure 367391DEST_PATH_IMAGE002
Adding deionized water to separate out precipitate;
Figure 100002_DEST_PATH_IMAGE006
collecting step
Figure 247753DEST_PATH_IMAGE004
Washing the precipitate with deionized water until the washed deionized water is neutral;
Figure 100002_DEST_PATH_IMAGE008
and drying to obtain the purified perylene bisimide or perylene bisimide powder.
Compared with the prior art, the invention has the advantages that: according to the solid aluminum electrolytic capacitor and the preparation method thereof, the PEDOT and PSS high polymer is doped by the perylene bisimide or the perylene bisimide, so that the conductivity of the doped PEDOT and PSS film formed in the core package is high, and meanwhile, the perylene bisimide or the perylene bisimide can prevent the oxidation of the PEDOT and PSS film by oxygen to a certain extent, so that the stability of the solid aluminum electrolytic capacitor is improved.
Detailed Description
In order to facilitate an understanding of the invention, the invention will now be described more fully and in detail with reference to the preferred embodiments, but the scope of the 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," secured to, "connected to or communicated with" another element, it can be directly fixed to, secured to, connected to or communicated with the other element or indirectly fixed to, secured to, connected to or communicated with the other element through other intermediate connecting members.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Example 1
A solid-state aluminum electrolytic capacitor with good stability comprises a shell and a core package, wherein the core package is arranged in the shell in a sealing mode through a rubber plug and comprises an anode foil, electrolytic paper and a cathode foil, a conductive high polymer is formed between the anode foil and the cathode foil, and the conductive high polymer contains a perylene imide doped PEDOT (Poly ethylene terephthalate): PSS (Poly styrene). In this embodiment, the core package is impregnated with the dispersion of the conductive polymer for 3 times, and the dispersion of the conductive polymer impregnated by the core package for the first time is PEDOT, PSS, dispersion without any doping; the dispersions of the conductive high molecular polymer impregnated at the 2 nd and 3 rd times are dispersions of perylene bisimide doped PEDOT (PSS). In the dispersion liquid of the perylene imide doped PEDOT PSS, the weight of the perylene imide is 8 percent of that of the PEDOT PSS.
In the embodiment, the perylene imide can cause a certain agglomeration phenomenon to occur on the PEDOT/PSS film, and the agglomeration phenomenon can cause a phenomenon that the resistance of the PEDOT/PSS film is not uniform, so that the electrical property of the solid aluminum electrolytic capacitor is influenced. The PEDOT (PSS) film doped with perylene diimide is agglomerated to cause the phenomenon of nonuniform resistance due to the PSS dispersion liquid; in this embodiment, the core package is first impregnated with undoped PEDOT, PSS dispersion and formed into a thin film, which can effectively alleviate this phenomenon.
In the embodiment, the conductivity of the perylene imide doped PEDOT/PSS film is higher than that of the undoped PEDOT/PSS film, so that the internal resistance of the solid-state aluminum electrolytic capacitor can be effectively reduced. However, if the doping amount of the perylene imide is too large, for example, more than 10% of the weight of the PEDOT: PSS, the conductivity is reduced due to agglomeration of the perylene imide.
In the embodiment, when the core pack is produced, water vapor in the air enters the core pack, particularly after the core pack is dried by soaking doped PEDOT. And in the charge-discharge cycle of the solid capacitor, the water vapor in the core bag firstly reacts with the perylene bisimide due to the oxygen generated by the electrolytic water, so that the PEDOT (PSS) film is protected from being oxidized by the oxygen and is separated from the anode foil, and the normal use of the capacitor is ensured.
The embodiment also provides a preparation method of the solid-state aluminum electrolytic capacitor with good stability, which comprises the following steps:
1) the perylene bisimide is uniformly dispersed in the DMSO solvent to form a dispersion. The perylene bisimide in the step 1) is purified perylene bisimide powder, and the purification step comprises
Figure 921180DEST_PATH_IMAGE002
Dissolving perylene bisimide or perylene bisimide powder in concentrated sulfuric acid under ultrasonic stirring;
Figure 41845DEST_PATH_IMAGE004
at the step of
Figure 105616DEST_PATH_IMAGE002
Adding deionized water to separate out precipitate;
Figure 366833DEST_PATH_IMAGE006
step of Collection
Figure 98029DEST_PATH_IMAGE004
Washing the precipitate with deionized water until the washed deionized water is neutral;
Figure 525948DEST_PATH_IMAGE008
and drying to obtain the purified perylene bisimide or perylene bisimide powder.
2) Adding PEDOT and PSS into the dispersion liquid in the step 1), wherein the weight concentration of the PEDOT and PSS in the dispersion liquid is 4%; the weight of the perylene bisimide or the perylene bisimide is 8 percent of the weight of PEDOT to PSS;
3) soaking undoped PEDOT in the core bag, namely PSS dispersion liquid, and drying; the weight concentration of PEDOT to PSS in the undoped PEDOT to PSS dispersion was 4%.
4) The core bag is impregnated with the dispersion liquid in the step 2), and a conductive high molecular polymer film is formed in the core bag after drying; repeat 2 times.
5) The core package is sealed in the shell through the rubber plug to form the solid aluminum electrolytic capacitor.
In the embodiment, the PEDOT/PSS high polymer is doped by the perylene bisimide or the perylene bisimide, so that the conductivity of the doped PEDOT/PSS film formed in the core package is higher, and meanwhile, the perylene bisimide can prevent the oxidation of the PEDOT/PSS film by oxygen to a certain extent, so that the stability of the solid aluminum electrolytic capacitor is improved.
Comparative example 1
In comparative example 1, the core was impregnated three times with the PEDOT: PSS dispersion, but the PEDOT: PSS dispersion was not doped at all, and the other portions were the same as in example 1.
The internal resistance and the capacitance retention rate after 8000 cycles of the internal resistance and the capacitance retention rate of the product of the embodiment 1 and the product of the comparative example 1 are randomly selected and respectively detected, and the result shows that the average internal resistance of the solid-state aluminum electrolytic capacitor of the embodiment 1 is 36.8m omega, and the average internal resistance of the solid-state aluminum electrolytic capacitor of the comparative example 1 is 39.1 m omega, so that the perylene imide can reduce the internal resistance of the solid-state aluminum electrolytic capacitor to a certain extent. The average capacitance of the solid aluminum electrolytic capacitor of example 1 before the cycle test was 138.7 μ F, the retention ratio of the capacitance after 8000 cycles was 92.8%, and 20 capacitors did not have a capacitance cliff drop. In comparative example 1, the average capacitance before the cycle test was 138.3 μ F, and in the surge test of the charge-discharge cycle, the capacitance of one solid aluminum electrolytic capacitor had fallen in a cliff-like manner and was discarded; after 19 solid-state aluminum electrolytic capacitors are left for 8000 cycles, the capacity retention rate is 88.5%.

Claims (8)

1. The utility model provides a good solid-state aluminum electrolytic capacitor of stability, includes shell and core package, the core package passes through the sealed setting of rubber buffer in the shell, the core package includes anode foil, electrolytic paper and cathode foil, be formed with electrically conductive high molecular polymer, its characterized in that between anode foil and the cathode foil: the conductive high polymer comprises perylene bisimide or perylene bisimide doped PEDOT, namely PSS thin film.
2. The solid aluminum electrolytic capacitor with good stability as set forth in claim 1, wherein: the perylene diimide or the perylene diimide accounts for 3% -10% of the weight of PEDOT and PSS.
3. The solid-state aluminum electrolytic capacitor with good stability according to claim 1, characterized in that: the core bag is impregnated with a dispersion liquid of a conductive high molecular polymer for multiple times, and the dispersion liquid of the conductive high molecular polymer impregnated by the core bag for the first time is PEDOT (PolyEthylenediisocyanate) (PSS) dispersion liquid; the dispersion liquid of the conductive high molecular polymer impregnated for the (N + 1) th time is perylene bisimide or perylene bisimide doped PEDOT, namely PSS dispersion liquid, wherein N is more than or equal to 1 and less than 4.
4. A preparation method of a solid-state aluminum electrolytic capacitor with good stability is characterized by comprising the following steps: the method comprises the following steps:
1) uniformly dispersing perylene bisimide or perylene bisimide in a solvent;
2) adding PEDOT and PSS into the dispersion liquid in the step 1), wherein the weight concentration of the PEDOT and PSS in the dispersion liquid is not more than 8%; the weight of the perylene diimide or the perylene diimide is 3 to 10 percent of that of PEDOT (PSS);
3) the core bag is impregnated with the dispersion liquid in the step 2), and a conductive high molecular polymer film is formed in the core bag after drying;
4) the core package is sealed in the shell through the rubber plug to form the solid aluminum electrolytic capacitor.
5. The method for preparing a solid-state aluminum electrolytic capacitor with good stability according to claim 4, characterized in that: the core package is impregnated with the dispersion of step 2) multiple times.
6. The method for preparing a solid-state aluminum electrolytic capacitor with good stability according to claim 4, characterized in that: and (3) before the step 3), the core bag is impregnated with PEDOT and PSS dispersion liquid, and the core bag is dried and formed with a PEDOT and PSS film.
7. The method for preparing a solid-state aluminum electrolytic capacitor with good stability according to claim 4, characterized in that: the solvent comprises one or more of DMSO, ethylene glycol, glycerol, NMP, resin, PVDF, xylene and methanol.
8. The method for manufacturing a solid aluminum electrolytic capacitor with good stability according to claim 4, wherein the method comprises the following steps: the perylene bisimide or perylene bisimide in the step 1) is purified before being added into a solvent, and the purification step comprises
Figure DEST_PATH_IMAGE002
Dissolving perylene bisimide or perylene bisimide powder in concentrated sulfuric acid under ultrasonic stirring;
Figure DEST_PATH_IMAGE004
in the step of
Figure 229168DEST_PATH_IMAGE002
Adding deionized water to separate out precipitate;
Figure DEST_PATH_IMAGE006
collecting step
Figure 834724DEST_PATH_IMAGE004
Washing the precipitate with deionized water until the washed deionized water is neutral;
Figure DEST_PATH_IMAGE008
drying to obtain the purified perylene bisimideOr perylene diimide powders.
CN202210498069.6A 2022-05-09 2022-05-09 Solid aluminum electrolytic capacitor with good stability and preparation method thereof Active CN114927348B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016187326A1 (en) * 2015-05-18 2016-11-24 The Johns Hopkins University Thermoelectric polymer composites
CN108766769A (en) * 2018-05-17 2018-11-06 湖南艾华集团股份有限公司 A kind of capacitor and preparation method thereof based on microwave curing gelular ion electrolyte
CN112071647A (en) * 2020-09-21 2020-12-11 湖南艾华集团股份有限公司 Solid-state aluminum electrolytic capacitor with good cycle performance and preparation method thereof
CN112735832A (en) * 2020-12-24 2021-04-30 湖南艾华集团股份有限公司 Medium-high voltage solid aluminum electrolytic capacitor and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016187326A1 (en) * 2015-05-18 2016-11-24 The Johns Hopkins University Thermoelectric polymer composites
CN108766769A (en) * 2018-05-17 2018-11-06 湖南艾华集团股份有限公司 A kind of capacitor and preparation method thereof based on microwave curing gelular ion electrolyte
CN112071647A (en) * 2020-09-21 2020-12-11 湖南艾华集团股份有限公司 Solid-state aluminum electrolytic capacitor with good cycle performance and preparation method thereof
CN112735832A (en) * 2020-12-24 2021-04-30 湖南艾华集团股份有限公司 Medium-high voltage solid aluminum electrolytic capacitor and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANHUA JIA等: ""Utilizing perylene diimmide as dopant to improve thermoelectric performance of PEDOT:PSS films"", 《COMPOSITES COMMUNICATIONS》 *

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