CN103578773B - A kind of capacitor cathode paper tinsel and capacitor and preparation method thereof - Google Patents

A kind of capacitor cathode paper tinsel and capacitor and preparation method thereof Download PDF

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CN103578773B
CN103578773B CN201310549038.XA CN201310549038A CN103578773B CN 103578773 B CN103578773 B CN 103578773B CN 201310549038 A CN201310549038 A CN 201310549038A CN 103578773 B CN103578773 B CN 103578773B
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capacitor
conductive polymer
optionally substituted
metal
layer
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CN103578773A (en
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覃九三
赵大成
刘春华
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Shenzhen Capchem Technology Co Ltd
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Shenzhen Capchem Technology Co Ltd
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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
    • 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
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • 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

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention discloses a kind of capacitor cathode paper tinsel, from the inside to the outside respectively oxidizable metal layer, metal oxide layer and dielectric substrate, the material of described oxidizable metal layer is valve metal or tantalum, niobium, aluminum, titanium, zirconium, hafnium, the alloy of vanadium and compound；Described dielectric substrate is the solid electrolyte containing conducting polymer, and described conducting polymer is the repetitive with logical formula I or (II), or the polythiophene of the repetitive of logical formula I and (II).Also disclose a kind of capacitor and the preparation method of this capacitor cathode paper tinsel thereof, the invention have the benefit that capacitor cathode paper tinsel of the present invention porous metal one layer of novel conductive polymer of medium of oxides layer overlying at high-specific surface area, this layer of conducting polymer structures densification, adhesion-tight is stable, there is good electric conductivity and contact with metal oxide dielectric film well, and while keeping solid electrolytic capacitor good characteristic, improve its high frequency performance by changing electrode material.

Description

Capacitor cathode foil, capacitor and preparation method thereof
Technical Field
The invention relates to a capacitor cathode material and a preparation method thereof, in particular to a capacitor cathode foil, a capacitor and a preparation method thereof.
Background
The semiconductor material MnO2 is used as the cathode of the aluminum or tantalum capacitor, so that the capacitor has great structural progress, and the problem of failure of the capacitor caused by electrolyte leakage, dryness and other factors is fundamentally solved. And the solid electrolyte capacitor has better temperature frequency characteristics in the electrolytic capacitor. Meanwhile, the capacitor meets the development direction of component chip type due to various shapes, so that the performance of the electrolytic capacitor reaches a new level by taking the solid electrolyte MnO2 as the cathode material of the aluminum or tantalum electrolytic capacitor.
The capacitor is required to be small, chip, large in capacity, low in equivalent series resistance, low in loss tangent, and high in frequency performance. As the MnO2 is used as a cathode material, the MnO has many process links and low conductivity (about 1S/cm) so that good high-frequency characteristics are difficult to obtain, and therefore, the equivalent series resistance Res of the solid capacitor is large, and the requirement of increasing high frequency of the current circuit cannot be met. The use of higher conductivity materials as the cathode of electrolytic capacitors has become a trend in the development of electrolytic capacitors.
Owing to their high electrical conductivity, pi-conjugated polymers are particularly suitable for use as solid electrolytes. Pi-conjugated polymers are also known as conducting polymers or synthetic metals. The importance of pi-conjugated polymers in terms of economy is increasing due to the advantages of polymers compared to metals in terms of the targeted adjustment of processability, weight and chemical modification properties. Examples of known pi-conjugated polymers are polypyrrole, polyaniline, polyacetylene, polyphenylacetylene, polythiophene. The novel conductive polymer poly (3, 4-ethylenedioxythiophene) has good environmental stability, the conductivity is very stable within the temperature range of-60-120 ℃, the conductivity is not influenced by climate temperature, and the conductivity (1-500S/cm) is much higher than that of MnO2, TCNQ composite salt, polyaniline and polypyrrole, and when the novel conductive polymer poly (3, 4-ethylenedioxythiophene) is used as a cathode material of a capacitor, the Res of the capacitor can be effectively reduced, and the impedance-frequency and capacity-frequency characteristics of the capacitor are improved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a capacitor cathode foil and a preparation method thereof.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a capacitor cathode foil comprises an oxidizable metal layer, a metal oxide layer and an electrolyte layer from the inside to the outside,
the oxidizable metal layer is made of valve metal or alloy and compound of tantalum, niobium, aluminum, titanium, zirconium, hafnium and vanadium;
the electrolyte layer is a solid electrolyte containing a conductive polymer, and the conductive polymer is polythiophene with a repeating unit shown in a general formula (I) or (II) or repeating units shown in the general formulae (I) and (II);
wherein,
a represents an optionally substituted C1-C5 alkylene group;
r represents a linear or branched optionally substituted C1-C18 alkyl group, an optionally substituted C5-C12 cycloalkyl group, an optionally substituted C6-C14 aryl group, an optionally substituted C7-C18 aralkyl group, an optionally substituted C1-C4 hydroxyalkyl group or a hydroxyl group;
x represents an integer of 0 to 8;
the conductive polymer is coated on the metal oxide layer by an electrochemical polymerization method to form a conductive polymer film, and the thickness of the conductive polymer film is 100-1000 μm.
Wherein the conductive polymer is polythiophene, polypyrrole or polyaniline.
Wherein the conductive polymer is poly (3, 4-ethylenedioxythiophene).
In order to achieve the purpose of the invention, the invention adopts another technical scheme that:
a capacitor comprises a cathode foil, wherein the cathode foil is respectively provided with an oxidizable metal layer, a metal oxide layer and an electrolyte layer from inside to outside;
the oxidizable metal layer is made of valve metal or alloy and compound of tantalum, niobium, aluminum, titanium, zirconium, hafnium and vanadium;
the electrolyte layer is a solid electrolyte containing a conductive polymer, and the conductive polymer is polythiophene with a repeating unit shown in a general formula (I) or (II) or repeating units shown in the general formulae (I) and (II);
wherein,
a represents an optionally substituted C1-C5 alkylene group;
r represents a linear or branched optionally substituted C1-C18 alkyl group, an optionally substituted C5-C12 cycloalkyl group, an optionally substituted C6-C14 aryl group, an optionally substituted C7-C18 aralkyl group, an optionally substituted C1-C4 hydroxyalkyl group or a hydroxyl group;
x represents an integer of 0 to 8;
the conductive polymer is coated on the metal oxide layer by an electrochemical polymerization method to form a conductive polymer film, and the thickness of the conductive polymer film is 100-1000 μm.
In order to achieve the above object, the present invention adopts another technical solution as follows:
a preparation method of a capacitor cathode foil comprises the following steps:
1) selecting valve metal or alloy and compound of tantalum, niobium, aluminum, titanium, zirconium, hafnium and vanadium as oxidizable metal layer;
2) selecting an oxide capable of oxidizing the metal in the step 1 as a metal oxide layer;
3) covering a metal oxide layer with a conductive polymer by adopting an electrochemical polymerization method, wherein the conductive polymer is polythiophene with a repeating unit shown in a general formula (I) or (II) or repeating units shown in the general formulas (I) and (II);
wherein,
a represents an optionally substituted C1-C5 alkylene group;
r represents a linear or branched optionally substituted C1-C18 alkyl group, an optionally substituted C5-C12 cycloalkyl group, an optionally substituted C6-C14 aryl group, an optionally substituted C7-C18 aralkyl group, an optionally substituted C1-C4 hydroxyalkyl group or a hydroxyl group;
x represents an integer of 0 to 8;
the conductive polymer is coated on the metal oxide layer by an electrochemical polymerization method to form a conductive polymer film, the thickness of the conductive polymer film is 100-1000 mu m, and the polymerization time is 150-500 s.
Wherein, the electrochemical oxidation polymerization in the step 3) is carried out at the temperature of-85 ℃ to 320 ℃ of the boiling point of the solvent.
Wherein, an electrolyte additive is further added into the solution before the midpoint chemical oxidative polymerization in the step 3), and the electrolyte additive is free acid.
Wherein the free acids are p-toluenesulfonic acid, methanesulfonic acid and salts with alkanesulfonates, aromatic sulfonates, tetrafluoroborates, hexafluorophosphates, perchlorates, hexafluoroantimonates, hexafluoroarsenates and hexafluoroantimonate anions and alkali metal, alkaline earth metal or optionally alkylated ammonium, phosphonium, sulfonium and oxonium cations.
The invention has the beneficial effects that: the capacitor cathode foil is characterized in that a porous metal oxide dielectric layer with high specific surface area is coated with a layer of novel conductive polymer, the layer of conductive polymer has a compact structure, is firmly and stably attached, has good conductivity and is well contacted with the metal oxide dielectric layer, and the high-frequency performance of the solid electrolytic capacitor is improved by changing an electrode material while the excellent characteristics of the solid electrolytic capacitor are kept, so that the thickness of the conductive polymer film is controlled to be 100-1000 mu m because the mechanical strength of the conductive polymer film is insufficient when the thickness of the conductive polymer film is less than 100 mu m, the subsequent processing is not facilitated, on the other hand, the resistance of the conductive polymer film is increased, and the ESR (equivalent series resistance) of; when the thickness of the conductive polymer film is more than 1000 μm, the adhesive strength between the conductive polymer and the aluminum foil is not high, the conductive polymer layer is liable to fall off and crack, the conductive performance is deteriorated, and the ESR of the manufactured capacitor is also increased.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the present invention in detail, the following description is given in detail with reference to the embodiments.
The capacitor cathode foil of the present invention is used as a solid electrolytic capacitor cathode or a supercapacitor cathode.
The foil for a capacitor cathode obtained according to the present invention comprises:
a layer of an oxidizable metal, the layer comprising,
a layer of an oxide of the metal, a metal oxide,
a layer of a solid electrolyte comprising a conductive polymer,
characterized in that the oxidizable metal is a valve metal or a compound with comparable properties, characterized in that the valve metal or the compound with comparable properties is tantalum, niobium, aluminum, titanium, zirconium, hafnium, vanadium, an alloy or a compound of at least one of these metals with another element.
The conductive polymer contained in the solid electrolyte is polythiophene with a repeating unit of a general formula (I) or (II) or repeating units of the general formulae (I) and (II).
Wherein A represents an optionally substituted C1-C5 alkylene group,
r represents a linear or branched optionally substituted C1-C18 alkyl group, an optionally substituted C5-C12 cycloalkyl group, an optionally substituted C6-C14 aryl group, an optionally substituted C7-C18 aralkyl group, an optionally substituted C1-C4 hydroxyalkyl group or a hydroxyl group,
x represents an integer from 0 to 8, which may be identical or different if a plurality of radicals R are attached to A.
The conductive polymer in the solid electrolyte is coated on the metal oxide dielectric layer by an electrochemical oxidative polymerization method. The thickness of the conductive polymer film coated on the metal oxide dielectric layer is 100 to 1000 μm. During electrochemical polymerization, a thin layer of conductive polymer may be first coated on a metal oxide dielectric layer. After applying a voltage to the layer, a layer containing the conductive polymer grows thereon. The electrochemical oxidative polymerization of the precursor can be carried out at a temperature of-85 ℃ to the boiling point of the solvent used. The electrochemical polymerization is preferably carried out at a temperature of from-85 ℃ to 320 ℃, preferably from-40 ℃ to 70 ℃, particularly preferably at room temperature. Depending on the precursor used, the electrolyte used, the temperature selected and the current density applied, the time of the electrochemical polymerization reaction is from 10 seconds to 30 hours, preferably from 60 seconds to 1 hour, particularly preferably from 100 seconds to 30 minutes. If the precursor is a liquid, electropolymerization may be carried out in the presence or absence of an aqueous or nonaqueous solvent which is inert under the electropolymerization conditions. The electropolymerization of the solid precursor is carried out in the presence of a solvent which is inert under the electrochemical polymerization conditions. In some cases it is advantageous to use a solvent mixture and/or to add a solubilizer (detergent) to the solvent. Solvents in aqueous or non-aqueous phase which are inert under electropolymerization conditions include: water; alcohols such as methanol and ethanol; ketones, such as acetone; chlorinated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and fluorinated hydrocarbons; esters, such as ethyl acetate and butyl acetate; carbonates such as propylene carbonate; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane; nitriles such as acetonitrile and benzonitrile; sulfoxides, such as dimethyl sulfoxide; sulfones, such as dimethyl sulfone, phenyl methyl sulfone, and sulfolane; liquid aliphatic amides such as methylacetamide, dimethylacetamide, dimethylformamide, pyrrolidone, N-methylpyrrolidone, N-methylcaprolactam; aliphatic and mixed aliphatic-aromatic ethers, such as diethyl ether, diethyl ether and anisole; liquid ureas, such as tetramethylurea or N, N-dimethylimidazolidinone. To perform the electropolymerization, an electrolyte additive is added to the precursor or a solution thereof. Free acids or conventional carrier electrolytes having a certain solubility in the solvents used are preferably used as electrolyte additives. The following have been demonstrated as electrolyte additives: free acids, for example p-toluenesulfonic acid, methanesulfonic acid and salts with alkanesulfonates, aromatic sulfonates, tetrafluoroborates, hexafluorophosphates, perchlorates, hexafluoroantimonates, hexafluoroarsenates and hexafluoroantimonate anions and alkali metal, alkaline earth metal or optionally alkylated ammonium, phosphonium, sulfonium and oxonium cations. The concentration of the precursor may be 0.01 to 100 wt%, said concentration preferably being 0.05 to 30%.
The electropolymerization can be carried out batchwise or continuously. The method for electropolymerization may be galvanostatic, potentiostatic, cyclic voltammetry. Wherein the current density can be varied within a wide range; a current density of 0.0001 to 120mA/cm3 is generally used, preferably 0.005 to 60mA/cm 3; the potential can also vary within a wide range, and a constant voltage potential of 0.1 to 100V is generally used, preferably 0.5 to 75V.
For metal oxide dielectrics, it is advantageous to electrochemically mimic the oxide film after electrochemical polymerization to modify defects that may be present in the oxide film and subsequently reduce the residual current of the finished capacitor. As counter-ion for the preparation of the conductive polymer, monomeric or polymeric anions can be mentioned, preferably anions of monomeric or polymeric sulfonic acids or naphthenic or aromatic sulfonic acids. The anions of the monomeric alkanesulfonic acids or cycloalkanesulfonic acids or aromatic sulfonic acids are particularly preferred for use in the electrolytic capacitors according to the invention, since the solutions containing them are more permeable into the dielectric-coated porous electrode material and thus allow a larger contact area to be formed between the dielectric and the solid electrolyte. The counter ion is added to the solution, for example in the form of its alkali metal salt or its free acid. These counterions are added to the precursor or precursor solution during electrochemical polymerization, optionally as electrolyte additives or a carrier electrolyte.
All electrolyte solutions can be deaerated without introducing or introducing nitrogen for 0-60 minutes before electropolymerization, and nitrogen can be slowly introduced or not introduced during the whole electropolymerization period so that the reaction is carried out under an inert atmosphere or a non-inert atmosphere.
Example 1:
the anodized aluminum anode is used as a working electrode, the foil is used as a counter electrode, and the electrochemical polymerization is carried out on the 3, 4-Ethylenedioxythiophene (EDOT) in boron trifluoride ether electrolyte solution under the constant potential polymerization condition of 1.5 mA. Wherein the EDOT monomer concentration was 0.01mol/L, the polymerization time was 180S, and the thickness of the electroconductive polymer film was found to be 120. mu.m.
Example 2:
the anodized aluminum anode is used as a working electrode, the foil is used as a counter electrode, and the electrochemical polymerization is carried out on the 3, 4-Ethylenedioxythiophene (EDOT) in a boron trifluoride diethyl etherate electrolyte solution with the concentration of 0.2g/L of sodium polystyrene sulfonate under the constant potential polymerization condition of 1.5 mA. Wherein the EDOT monomer concentration was 0.01mol/L, the polymerization time was 180S, and the thickness of the electroconductive polymer film was found to be 130. mu.m.
Example 3:
after nitrogen is introduced into an electrolytic cell containing 0.5mol/L potassium nitrate (KNO3) solution to remove oxygen, monomer 3, 4-Ethylenedioxythiophene (EDOT) is added, an anodized aluminum anode is taken as a working electrode, a foil is taken as a counter electrode, and the scanning is carried out for 20 times at a sweep rate of 50mV/s within the range of-0.80 to + 1.50V. Wherein the EDOT monomer concentration was 0.01mol/L, the thickness of the electroconductive polymer film was found to be 330. mu.m.
Example 4:
pure dry nitrogen is introduced into acetonitrile solution with the concentration of tetrabutyl ammonium perchlorate of 0.1mol/L to remove oxygen for 10 minutes, and electrochemical polymerization is carried out on 3, 4-Ethylenedioxythiophene (EDOT) under the condition of constant potential polymerization of 1mA under the nitrogen atmosphere by taking an anodized aluminum anode as a working electrode and a foil as a counter electrode. Wherein the EDOT monomer concentration was 0.01mol/L, the polymerization time was 300S, and the thickness of the electroconductive polymer film was determined to be 630. mu.m.
Example 5:
introducing nitrogen into an electrolytic cell containing 1.0mol/L lithium perchlorate (LiClO4) solution to remove oxygen, adding 3, 4-Ethylenedioxythiophene (EDOT) monomer, taking an anodized aluminum anode as a working electrode and a foil as a counter electrode, and carrying out electrochemical polymerization on the 3, 4-Ethylenedioxythiophene (EDOT) under the constant potential polymerization condition of 1.2 mA. Wherein the EDOT monomer concentration was 0.01mol/L, the polymerization time was 400S, and the thickness of the electroconductive polymer film was found to be 830. mu.m.
Example 6:
introducing nitrogen into an electrolytic cell containing 0.2mol/L sodium sulfate (Na2SO4) solution to remove oxygen, adding monomer 3, 4-Ethylenedioxythiophene (EDOT), taking an anodized aluminum anode as a working electrode and a foil as a counter electrode, and carrying out electrochemical polymerization on the 3, 4-Ethylenedioxythiophene (EDOT) under the constant potential polymerization condition of 1.4 mA. Wherein the EDOT monomer concentration was 0.01mol/L, the polymerization time was 200S, and the thickness of the electroconductive polymer film was measured to be 430. mu.m.
Example 7:
introducing nitrogen into an electrolytic cell containing 0.8mol/L sodium tetrafluoroborate (NaBF4) solution to remove oxygen, adding a monomer of 3, 4-Ethylenedioxythiophene (EDOT), taking an anodized aluminum anode as a working electrode and a foil as a counter electrode, and carrying out electrochemical polymerization on the 3, 4-Ethylenedioxythiophene (EDOT) under the constant potential polymerization condition of 1.3 mA. Wherein the EDOT monomer concentration was 0.01mol/L, the polymerization time was 500S, and the thickness of the electroconductive polymer film was found to be 1000. mu.m.
Example 8:
the anodized aluminum anode is used as a working electrode, the foil is used as a counter electrode, and the electrochemical polymerization is carried out on the 3, 4-Ethylenedioxythiophene (EDOT) under the constant potential polymerization condition of 1.3mA in boron trifluoride diethyl etherate electrolyte solution with the concentration of p-toluenesulfonic acid of 0.2 g/L. Wherein the EDOT monomer concentration was 0.01mol/L, the polymerization time was 280S, and the thickness of the electroconductive polymer film was found to be 500. mu.m.
Example 9:
the anodized aluminum anode is used as a working electrode, the foil is used as a counter electrode, and the electrochemical polymerization is carried out on the 3, 4-Ethylenedioxythiophene (EDOT) under the constant potential polymerization condition of 1.6mA in the electrolyte solution of lithium perchlorate (LiClO4) with the concentration of sodium polystyrene sulfonate of 0.2 g/L. Wherein the EDOT monomer concentration was 0.01mol/L, the polymerization time was 270S, and the thickness of the electroconductive polymer film was found to be 470. mu.m.
Example 10:
pure dry nitrogen is introduced into acetonitrile solution with the concentration of tetrabutyl ammonium perchlorate of 0.1mol/L to remove oxygen for 10 minutes, and electrochemical polymerization is carried out on 3, 4-Ethylenedioxythiophene (EDOT) under the condition of constant current polymerization of 10mA under the nitrogen atmosphere by taking an anodized aluminum anode as a working electrode and a foil as a counter electrode. Wherein the EDOT monomer concentration was 0.01mol/L, the polymerization time was 150S, and the thickness of the electroconductive polymer film was found to be 120. mu.m.
Comparative example 1:
immersing the anodized aluminum anode into an n-butyl alcohol solution with EDOT concentration of 24.35 wt% for 10 seconds, taking out and drying; then immersing into 1.0mol/L p-methyl benzene sulfonic acid molten iron solution of 0.1mol/L sodium dodecyl benzene sulfonate for 10 seconds, taking out and drying, and placing in the air to cool for 3 minutes; repeat the above steps 6 times.
Immersing the aluminum chip subjected to the steps into an n-butyl alcohol solution with EDOT concentration of 24.35 wt% for 10 seconds, taking out and drying; then immersing into 3.5mol/L p-methyl benzene sulfonic acid molten iron solution of 0.2mol/L sodium dodecyl benzene sulfonate for 10 seconds, taking out and drying, and placing in the air to cool for 3 minutes; repeat the above steps 6 times.
The aluminum chip was cleaned with deionized water.
Comparative example 2 is substantially the same as example except that the polymerization time was 50S and the thickness of the conductive polymer film was 45 μm.
Comparative example 3 is substantially the same as example except that the polymerization time was 800S and the thickness of the conductive polymer film was 1300 μm.
The capacitor elements obtained in the above examples and comparative examples were further assembled into a solid aluminum electrolytic capacitor, and table 1 shows the respective performance values of the solid aluminum electrolytic capacitor obtained from the above capacitor elements.
TABLE 1 solid aluminium electrolytic capacitor Properties
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (4)

1. The preparation method of the capacitor cathode foil is characterized by comprising the following steps of:
1) selecting valve metal or alloy and compound of tantalum, niobium, aluminum, titanium, zirconium, hafnium and vanadium as oxidizable metal layer;
2) selecting an oxide capable of oxidizing the metal in the step 1 as a metal oxide layer;
3) covering a metal oxide layer with a conductive polymer by adopting an electrochemical polymerization method, wherein the conductive polymer is polythiophene with a repeating unit shown in a general formula (I) or (II) or repeating units shown in the general formulas (I) and (II);
wherein,
a represents an optionally substituted C1-C5 alkylene group;
r represents a linear or branched optionally substituted C1-C18 alkyl group, an optionally substituted C5-C12 cycloalkyl group, an optionally substituted C6-C14 aryl group, an optionally substituted C7-C18 aralkyl group, an optionally substituted C1-C4 hydroxyalkyl group or a hydroxyl group;
x represents an integer of 0 to 8;
the conductive polymer is coated on the metal oxide layer by an electrochemical polymerization method to form a conductive polymer film, the thickness of the conductive polymer film is 100-1000 mu m, and the polymerization time is 150-500 s.
2. The method for preparing a capacitor cathode foil according to claim 1, wherein the electrochemical polymerization process in step 3) is performed at a temperature of-85 ℃ to 320 ℃.
3. The method for preparing a capacitor cathode foil according to claim 1, wherein an electrolyte additive is further added to the solution before the electrochemical oxidative polymerization in the step 3), and the electrolyte additive is a free acid.
4. The method of claim 3, wherein the free acid is p-toluenesulfonic acid, methanesulfonic acid and alkanesulfonates, aromatic sulfonates, tetrafluoroborates, hexafluorophosphates, perchlorates, hexafluoroantimonates, hexafluoroarsenates and salts of hexafluoroantimonate anions and alkali metal, alkaline earth metal or optionally alkylated ammonium, phosphonium, sulfonium and oxonium cations.
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CN104409213A (en) * 2014-11-12 2015-03-11 深圳新宙邦科技股份有限公司 Electrolyte glue solution for post-treatment of formed foil, electrode foil and capacitor
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