CN112735834B - Novel solid-state aluminum electrolytic capacitor and preparation method thereof - Google Patents
Novel solid-state aluminum electrolytic capacitor and preparation method thereof Download PDFInfo
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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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- aluminum electrolytic
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- 239000003990 capacitor Substances 0.000 title claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title description 8
- 239000011888 foil Substances 0.000 claims abstract description 66
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 26
- 239000004917 carbon fiber Substances 0.000 claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229920000223 polyglycerol Polymers 0.000 claims description 14
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000003487 electrochemical reaction Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 17
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 241001089723 Metaphycus omega Species 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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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
- H01G9/15—Solid electrolytic capacitors
- H01G9/151—Solid electrolytic capacitors with wound foil electrodes
-
- 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
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/0425—Electrodes or formation of dielectric layers thereon characterised by the material specially adapted for cathode
-
- 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
- H01G9/04—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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Cell Electrode Carriers And Collectors (AREA)
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
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;
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.
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| CN202011600249.8A CN112735834B (en) | 2020-12-29 | 2020-12-29 | Novel solid-state aluminum electrolytic capacitor and preparation method thereof |
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| CN202011600249.8A CN112735834B (en) | 2020-12-29 | 2020-12-29 | Novel solid-state aluminum electrolytic capacitor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 application of polypyrrole/conductive carbon cloth composite 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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