CN113380550A - Method for preparing conductive polymer cathode in solid-state aluminum electrolytic capacitor - Google Patents
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000003990 capacitor Substances 0.000 title claims abstract description 56
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 30
- 239000011888 foil Substances 0.000 claims abstract description 64
- 239000007787 solid Substances 0.000 claims abstract description 29
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000002848 electrochemical method Methods 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229920000128 polypyrrole Polymers 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 8
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- 239000000243 solution Substances 0.000 description 19
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
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- 238000011065 in-situ storage Methods 0.000 description 1
- WHRAZOIDGKIQEA-UHFFFAOYSA-L iron(2+);4-methylbenzenesulfonate Chemical compound [Fe+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 WHRAZOIDGKIQEA-UHFFFAOYSA-L 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012808 vapor phase Substances 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
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
-
- 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
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
-
- 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
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- Microelectronics & Electronic Packaging (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明公开了一种在固态铝电解电容器中制备导电聚合物阴极的方法，属于固态铝电解电容器领域。包括：采用化学气相沉积法在阳极箔介质层表面预沉积导电层；在沉积的导电层表面采用电化学法制备导电聚合物，形成固态铝电解电容器中的复合导电层；对所述复合导电层进行阴极电极引出，即制得导电聚合物阴极。本发明所用的化学气相沉积技术避免了浸渍法和化学聚合法中溶液分子难以进入阳极铝箔表面微小孔洞的问题，同时有效避免了溶液对介质层的破坏。
The invention discloses a method for preparing a conductive polymer cathode in a solid aluminum electrolytic capacitor, and belongs to the field of solid aluminum electrolytic capacitors. The method includes: using chemical vapor deposition method to pre-deposit a conductive layer on the surface of the anode foil dielectric layer; using electrochemical method to prepare a conductive polymer on the surface of the deposited conductive layer to form a composite conductive layer in a solid aluminum electrolytic capacitor; Cathode electrode extraction is carried out to obtain a conductive polymer cathode. The chemical vapor deposition technology used in the invention avoids the problem that solution molecules are difficult to enter into tiny holes on the surface of the anode aluminum foil in the dipping method and the chemical polymerization method, and at the same time effectively avoids the damage of the solution to the dielectric layer.
Description
Technical Field
The invention relates to the field of solid aluminum electrolytic capacitors, in particular to a technology for preparing a conductive polymer film on the surface of an anode foil of a solid aluminum electrolytic capacitor by using a chemical vapor deposition method.
Background
The preparation of conductive cathodes in solid-state aluminum electrolytic capacitors is one of the major problems to be solved currently. The conductive polymer is the main material widely used as the cathode material of the solid aluminum electrolytic capacitor at present. The method for preparing the conductive polymer cathode film on the surface of the anode foil of the solid aluminum electrolytic capacitor comprises a dipping method, a chemical synthesis method, an electrochemical synthesis method and the like. In the dipping method, due to the influence of the surface tension and the molecular size of the solution, the molecules of the solution are difficult to enter tiny holes of the anode aluminum foil, the coverage of the conductive layer on the surface of the anode foil is influenced, and the capacity extraction rate of the capacitor is low; acidic substances, strong oxidants and the like contained in the solution of the chemical synthesis method can damage a dielectric layer on the surface of an anode foil of the aluminum electrolytic capacitor, so that the problems of reduced voltage resistance, increased leakage current and the like of the solid aluminum electrolytic capacitor are caused; the electrochemical method is to polymerize under the action of an external electric field to form a conductive layer, and has the advantages of strong controllability, excellent conductive performance and mechanical property of the synthesized polymer, and less damage to the anode foil dielectric layer caused by the solution of the electrochemical method than the chemical method. However, because of the insulating property of the dielectric layer on the surface of the capacitor anode foil, when the electrochemical method is used, it is necessary to prepare a conductive layer on the surface of the dielectric layer in advance by a thermal decomposition method or a chemical method. On this basis, the conductive polymer layer can only be produced using an electrochemical process. When a thermal decomposition method or a chemical method is used for preparing a pre-deposited conducting layer on an anode foil medium, the problems of damage of a solution to a dielectric layer, poor adhesion between the prefabricated conducting layer and the dielectric layer, low conductivity and the like exist, and the problems of reduced withstand voltage, increased leakage current, low capacity extraction rate and the like of a final solid capacitor are caused.
Through research on documents, in 2011, polypyrrole is prepared by strongly adopting a chemical oxidation method and an electrochemical method as a conductive cathode of a solid aluminum electrolytic capacitor. In 1996, Yasuo Kudoh et al prepared polypyrrole as a conductive cathode of a solid-state aluminum electrolytic capacitor by using manganese oxide pyrolysis and an electrochemical method. In comparison with the above literature reports, we find a common point that the liquid phase method is adopted to prepare the pre-conductive layer when the solid-state aluminum electrolytic capacitor is prepared by the current method, and then the electrochemical method is used to prepare the polymer conductive layer. The capacitor prepared in this way has low capacity extraction amount, and large equivalent series resistance and loss.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a method for preparing a conductive polymer cathode in a solid-state aluminum electrolytic capacitor.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a method for preparing a conductive polymer cathode in a solid-state aluminum electrolytic capacitor, which is characterized in that,
pre-depositing a conductive layer on the surface of the anode foil dielectric layer by adopting a chemical vapor deposition method;
preparing a conductive polymer on the surface of the deposited conductive layer by adopting an electrochemical method to form a composite conductive layer in the solid-state aluminum electrolytic capacitor;
and leading out a cathode electrode of the composite conductive layer to obtain a conductive polymer cathode.
Preferably, the anode foil is a porous aluminum foil with a dielectric layer.
Preferably, the pre-deposited conductive layer is a conductive layer formed using chemical vapor deposition.
Preferably, the pre-deposited conductive layer is made of a conductive carbon material.
Further preferably, the conductive carbon material is selected from carbon nanotubes and/or graphene.
Preferably, the conductive polymer comprises one or more of polypyrrole, polyaniline and poly 3, 4-ethylenedioxythiophene.
Preferably, conducting carbon paste, silver paste, aluminum foil or silver wires are adopted to lead out the cathode electrode of the composite conducting layer.
Preferably, the anode foil is adjustable in geometric area size.
Compared with the prior art, the invention has the following beneficial effects:
1. the chemical vapor deposition technology used by the invention avoids the problem that solution molecules are difficult to enter micro holes on the surface of the anode aluminum foil in an impregnation method and a chemical polymerization method, so that the conductive film has high step coverage rate in the micro-nano holes, and the capacity extraction rate of the capacitor is improved.
2. The damage of strong oxidant and strong acid substance in the solution to the aluminum foil medium layer is avoided.
3. The pre-deposited conductive layer prepared by the chemical vapor phase method has the advantages of less impurities, high conductivity, good uniformity and the like.
The pre-deposited conducting layer obtained by the chemical vapor deposition technology used in the invention has good adhesion with the dielectric layer, and can effectively avoid the damage to the dielectric layer when the composite conducting layer is subsequently prepared.
Drawings
FIG. 1 is a schematic structural diagram of a solid-state aluminum electrolytic capacitor;
FIG. 2 is a cross-sectional SEM image of an aluminum anode foil dielectric layer after a conductive layer has been pre-deposited thereon using a chemical vapor deposition technique;
table 1 shows the electrical performance parameters of solid aluminum capacitors prepared using this technique.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1 and fig. 2, the method for preparing a conductive polymer cathode in a solid aluminum electrolytic capacitor disclosed by the invention adopts a chemical vapor deposition method to pre-deposit a conductive layer on the surface of an anode foil dielectric layer; preparing a conductive polymer on the surface of the deposited conductive layer by adopting an electrochemical method to form a composite conductive layer in the solid-state aluminum electrolytic capacitor; and leading out a cathode electrode of the composite conductive layer to obtain the conductive polymer cathode. In fig. 2, the white circles mean carbon materials deposited in advance.
And carrying out electrochemical performance tests on the conductive polymer cathode, wherein the electrochemical performance tests comprise tests of capacitance, loss, leakage current, equivalent series resistance and the like of the capacitor.
Comparative example 1
(1) Preparation work: and cutting the anode foil with the anode leading-out end by using an aluminum foil cutting die, and supplementing the cut edge.
(2) The conductive layer is prepared by predepositing manganese oxide. The method specifically comprises the following steps: immersing the anode aluminum foil obtained after the treatment in the step (1) in a permanganate aqueous solution at 60 ℃, dropwise adding methanol and a 0.1M nitric acid solution, mixing and heating for 30min, and taking out the anode aluminum foil with the manganese oxide layer.
(3) The conductive layer is prepared by an electrochemical method. The method specifically comprises the following steps: under room temperature and normal pressure, a constant current method (j is less than or equal to 5 mA-cm)-2Potential of 1V (relative to SCE)), electropolymerization is carried out on the anode aluminum foil obtained after the treatment of the step (2) in a solution containing 0.5M pyrrole monomer and 0.5M triisopropyl naphthalene sulfonate (TIPNS). And depositing a layer of polypyrrole on the surface of the carbon nano tube conductive layer to form a composite conductive layer in the solid-state aluminum electrolytic capacitor.
(4) And (3) dripping a layer of conductive carbon paste on the surface of the anode foil obtained in the step (2), solidifying at room temperature, dripping silver paste, and placing silver wires as cathode leading-out terminals.
The electrical performance parameters of the prepared solid aluminum electrolytic capacitor are tested as follows: 69% capacitance bleed; 5.5% loss; 6 omega equivalent series resistance; 0.2mA leakage current.
Comparative example 2
(1) Preparation work: and cutting the anode foil with the anode leading-out end by using an aluminum foil cutting die, and supplementing the cut edge.
(2) The cathode conductive layer is prepared by in-situ polymerization. The method specifically comprises the following steps: respectively immersing the anode foil obtained after the treatment in the step (1) into a 3, 4-ethylenedioxythiophene solution (EDOT) and an iron p-toluenesulfonate solution; taking out and drying.
(3) The conductive layer is prepared by an electrochemical method. The method specifically comprises the following steps: under room temperature and normal pressure, a constant current method (j is less than or equal to 5 mA-cm)-2Potential of 1V (relative to SCE)), electropolymerization is carried out on the anode aluminum foil obtained after the treatment of the step (2) in a solution containing 0.5M pyrrole monomer and 0.5M triisopropyl naphthalene sulfonate (TIPNS). And depositing a layer of polypyrrole on the surface of the carbon nano tube conductive layer to form a composite conductive layer in the solid-state aluminum electrolytic capacitor.
(4) And (3) dripping a layer of conductive carbon paste on the surface of the anode foil obtained in the step (2), solidifying at room temperature, dripping silver paste, and placing silver wires as cathode leading-out terminals.
The electrical performance parameters of the prepared solid aluminum electrolytic capacitor are tested as follows: 70% capacitance bleed; 4% loss; 3 Ω equivalent series resistance; 0.17mA leakage current.
Example 1
(1) Preparation work: cutting 1 x 1cm with anode lead out using aluminum foil cutting die2The anode foil with the geometric area is formed by complementing the cutting edge.
(2) The carbon nanotube conductive layer is deposited by Chemical Vapor Deposition (CVD). The method specifically comprises the following steps: and (3) putting the aluminum foil obtained after the treatment in the step (1) into the middle of a quartz boat, and pushing the aluminum foil into a quartz tube (with the length of 100 cm and the inner diameter of 35 cm). With acetylene (C)2H2) For carbon source gas, the carbon source gas is directly grown on an aluminum micro-grate by a chemical vapor deposition method in a horizontal tube furnace. Before heating to the set temperature (600 ℃), argon gas with a certain flow rate is introduced into the furnace for 30 minutes, and air is discharged. Carbon source C2H2The flow rate introduced into the furnace was 50ml min-1. After 15min growth, the tube furnaceThe mixture was cooled to room temperature under an argon atmosphere, and the aluminum foil was taken out.
(3) And preparing polypyrrole on the pre-deposited carbon nanotube layer by using an electrochemical method. The method specifically comprises the following steps: under room temperature and normal pressure, a constant current method (j is less than or equal to 5 mA-cm)-2Potential of 1V (relative to SCE)), electropolymerization is carried out on the anode aluminum foil obtained after the treatment of the step (2) in a solution containing 0.5M pyrrole monomer and 0.5M triisopropyl naphthalene sulfonate (TIPNS). And depositing a layer of polypyrrole on the surface of the carbon nano tube conductive layer to form a composite conductive layer in the solid-state aluminum electrolytic capacitor.
(4) And (4) dripping a layer of conductive carbon paste on the surface of the anode foil obtained in the step (3), solidifying at room temperature, dripping silver paste, and placing silver wires as a cathode leading-out terminal.
The electrical performance parameters of the solid aluminum electrolytic capacitor prepared in the embodiment are tested as follows: 83% capacitance pull-out; 5.0% loss; 5.0 omega equivalent series resistance; 0.004mA leakage current.
Example 2
(1) Preparation work: cutting 1 x 1cm with anode lead out using aluminum foil cutting die2The anode foil with the geometric area is formed by complementing the cutting edge.
(2) And growing a carbon nano tube conducting layer on the dielectric layer by a Chemical Vapor Deposition (CVD) technology. The method specifically comprises the following steps: and (2) putting the aluminum foil obtained after the treatment in the step (1) into the middle of a quartz boat, and pushing the aluminum foil into a quartz tube (with the length of 100 cm and the inner diameter of 35 cm). With acetylene (C)2H2) For carbon source gas, the carbon source gas is directly grown on an aluminum micro-grate by a chemical vapor deposition method in a horizontal tube furnace. Before heating to the set temperature (600 ℃), argon gas with a certain flow rate is introduced into the furnace for 30 minutes, and air is discharged. Carbon source C2H2The flow rate introduced into the furnace was 40ml min-1. After 20min growth, the tube furnace was cooled to room temperature under argon atmosphere and the aluminum foil was removed.
(3) And preparing polypyrrole on the pre-deposited carbon nanotube layer by using an electrochemical method. The method specifically comprises the following steps: under room temperature and normal pressure, a constant current method (j is less than or equal to 5 mA-cm)-2) The anode obtained after the treatment of the step (2)Aluminum foil was electropolymerized in a solution containing 0.5M pyrrole monomer and 0.5M triisopropylnaphthalene sulfonate (TIPNS). And depositing a layer of polypyrrole on the surface of the carbon nano tube conductive layer to form a composite conductive layer in the solid-state aluminum electrolytic capacitor.
(4) And (4) dripping a layer of conductive carbon paste on the surface of the anode foil obtained in the step (3), solidifying at room temperature, dripping silver paste, and placing silver wires as a cathode leading-out terminal.
The electrical performance parameters of the solid aluminum electrolytic capacitor prepared in the embodiment are tested as follows: 75% capacitance bleed; 3.8% loss; 3.2 omega equivalent series resistance; 0.002mA leakage current.
Example 3
(1) Preparation work: cutting 1 x 1cm with anode lead out using aluminum foil cutting die2The anode foil with the geometric area is formed by complementing the cutting edge.
(2) And growing a graphene conducting layer on the dielectric layer by a chemical vapor deposition technology. The method specifically comprises the following steps: putting the aluminum foil obtained after the treatment in the step (1) into the middle of a quartz boat, and pushing the aluminum foil into a quartz tube (with the length of 100 cm and the inner diameter of 35 cm); argon gas is continuously introduced, and benzene steam is introduced after 10 min. And (3) reacting at 400 ℃ for 30 minutes to obtain a graphene conducting layer, and taking out the graphene conducting layer after cooling to room temperature.
(3) Polypyrrole was prepared on the pre-deposited graphene conductive layer using an electrochemical method. The method specifically comprises the following steps: under room temperature and normal pressure, a constant current method (j is less than or equal to 5 mA-cm)-2Potential of 1V (relative to SCE)), electropolymerization is carried out on the anode aluminum foil obtained after the treatment of the step (2) in a solution containing 0.5M pyrrole monomer and 0.5M triisopropyl naphthalene sulfonate (TIPNS). And depositing a layer of polypyrrole on the surface of the titanium nitride to form a composite conductive layer in the solid-state aluminum electrolytic capacitor.
(4) And (4) dripping a layer of conductive carbon paste on the surface of the anode foil obtained in the step (3), solidifying at room temperature, dripping silver paste, and placing silver wires as a cathode leading-out terminal.
The electrical performance parameters of the solid aluminum electrolytic capacitor prepared in the embodiment are tested as follows: 79% capacitance bleed; 3.5% loss; 2.54 Ω equivalent series resistance; 0.002mA leakage current.
Example 4
(1) Preparation work: cutting 1 x 1cm with anode lead out using aluminum foil cutting die2The anode foil with the geometric area is formed by complementing the cutting edge.
(2) And growing a graphene conducting layer on the dielectric layer by a chemical vapor deposition technology. The method specifically comprises the following steps: putting the aluminum foil obtained after the treatment in the step (1) into the middle of a quartz boat, and pushing the aluminum foil into a quartz tube (with the length of 100 cm and the inner diameter of 35 cm); argon gas is continuously introduced, and benzene steam is introduced after 10 min. And reacting at 500 ℃ for 30 minutes to obtain the graphene conducting layer, and taking out the graphene conducting layer after cooling to room temperature.
(3) Polypyrrole was prepared on the pre-deposited graphene conductive layer using an electrochemical method. The method specifically comprises the following steps: under room temperature and normal pressure, a constant current method (j is less than or equal to 5 mA-cm)-2Potential of 1V (relative to SCE)), electropolymerization is carried out on the anode aluminum foil obtained after the treatment of the step (2) in a solution containing 0.5M pyrrole monomer and 0.5M triisopropyl naphthalene sulfonate (TIPNS). And depositing a layer of polypyrrole on the surface of the titanium nitride to form a composite conductive layer in the solid-state aluminum electrolytic capacitor.
(4) And (4) dripping a layer of conductive carbon paste on the surface of the anode foil subjected to the step (3), solidifying at room temperature, dripping silver paste, and placing silver wires as a cathode leading-out terminal.
The electrical performance parameters of the solid aluminum electrolytic capacitor prepared in the embodiment are tested as follows: 82.4% capacitance bleed; 4.2% loss; 4.60 Ω equivalent series resistance; 0.003mA leakage current.
The conductivity test of the cathode conductive film of the solid-state aluminum electrolytic capacitor prepared in the above embodiment is performed, and the obtained experimental results are shown in table 1 below:
table 1 electrical performance parameters of solid state aluminum capacitors prepared
From the results in table 1, it can be seen that the performance of the solid-state aluminum electrolytic capacitor obtained by the method of the present invention is greatly improved compared with the performance of the solid-state aluminum electrolytic capacitor obtained by the current pre-deposition and electrochemical preparation method.
In summary, the present invention proposes to use the chemical vapor deposition technology to prepare a pre-deposited cathode conductive layer on the surface of the aluminum electrolytic capacitor anode foil dielectric layer, and then use the electrochemical polymerization method to prepare a conductive polymer layer on the pre-deposited layer, so as to solve the problems existing in the prior art: (1) when the conducting layer is prepared by a chemical method and a pyrolysis method, the obtained film has low conductivity, and acidic substances and oxidants in the solution easily damage a dielectric layer on the surface of the anode foil, so that the voltage resistance and the leakage current property of the solid capacitor are deteriorated; (2) the conductive film layer has poor adhesion on the surface of the anode foil medium, resulting in large contact resistance and large loss of the capacitor.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
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| CN202110469804.6A CN113380550A (en) | 2021-04-28 | 2021-04-28 | Method for preparing conductive polymer cathode in solid-state aluminum electrolytic capacitor |
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| CN114316218A (en) * | 2021-11-29 | 2022-04-12 | 西安交通大学 | Preparation method of water-soluble conductive polymer and application of water-soluble conductive polymer in preparation of solid aluminum electrolytic capacitor |
| CN114974902A (en) * | 2022-06-22 | 2022-08-30 | 西安交通大学 | Method for preparing solid state valve metal electrolytic capacitor solid cathode by gas phase method |
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| JP2018046220A (en) * | 2016-09-16 | 2018-03-22 | ローム株式会社 | Solid electrolytic capacitor and method for manufacturing the same |
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| CN114316218A (en) * | 2021-11-29 | 2022-04-12 | 西安交通大学 | Preparation method of water-soluble conductive polymer and application of water-soluble conductive polymer in preparation of solid aluminum electrolytic capacitor |
| CN114974902A (en) * | 2022-06-22 | 2022-08-30 | 西安交通大学 | Method for preparing solid state valve metal electrolytic capacitor solid cathode by gas phase method |
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Application publication date: 20210910 |