CN108492988B - Solid-state capacitor cathode carbon foil and preparation method thereof, and solid-state capacitor and preparation method thereof - Google Patents
Solid-state capacitor cathode carbon foil and preparation method thereof, and solid-state capacitor and preparation method thereof Download PDFInfo
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- CN108492988B CN108492988B CN201810241635.9A CN201810241635A CN108492988B CN 108492988 B CN108492988 B CN 108492988B CN 201810241635 A CN201810241635 A CN 201810241635A CN 108492988 B CN108492988 B CN 108492988B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003990 capacitor Substances 0.000 title claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 80
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- 238000005260 corrosion Methods 0.000 claims abstract description 36
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- 238000000576 coating method Methods 0.000 claims abstract description 22
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- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 45
- 238000006116 polymerization reaction Methods 0.000 claims description 40
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- 238000001035 drying Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- SATJMZAWJRWBRX-UHFFFAOYSA-N azane;decanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCCCCCC([O-])=O SATJMZAWJRWBRX-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
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Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, 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
- H01G9/055—Etched 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
- H01G9/15—Solid electrolytic capacitors
- H01G9/151—Solid electrolytic capacitors with wound foil electrodes
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention provides a solid-state capacitor cathode carbon foil which comprises a corrosion aluminum foil and a conducting layer, wherein the conducting layer is coated on the surface of the corrosion aluminum foil, the conducting layer comprises a conducting high polymer layer and a carbon conducting layer, and the conducting high polymer layer is coated on the surface of the corrosion aluminum foil or the surface of the corrosion aluminum foil coated with the carbon conducting layer. According to the invention, a conductive polymer layer and a carbon conductive layer are coated on a conventional corrosion aluminum foil to obtain the solid-state capacitor cathode carbon foil with a simple structure, the solid-state capacitor cathode carbon foil can be prepared only by a conventional coating method, and the solid-state capacitor prepared by using the cathode foil has the advantages of high capacity, low loss and low ESR value.
Description
Technical Field
The invention relates to the field of capacitors, in particular to a solid-state capacitor cathode carbon foil and a preparation method thereof, and a solid-state capacitor and a preparation method thereof.
Background
The capacitor is formed of two electrodes and a dielectric material therebetween, and serves primarily as charge storage, filtering, coupling, tuning and oscillation. Specifically, the characteristics, functions and applications of capacitors with different structures are different, wherein the solid-state aluminum electrolytic capacitor cathode carbon foil obtained by taking the aluminum foil as a base film and compounding the graphite layer on the surface has the advantage of high capacitance, and is widely applied and popularized.
The cathode carbon foil of the solid aluminum electrolytic capacitor is mainly prepared by adopting a magnetron sputtering method at present, and in order to ensure that graphite is tightly combined with an aluminum foil, a layer of transition metal is firstly magnetron sputtered on the aluminum foil, and then a layer of graphite is magnetron sputtered on the outer layer of the transition metal. The negative electrode foil with the structure contains a transition metal layer, so that the preparation process is relatively complex, the energy consumption is high, heat treatment must be carried out in specific gas, the problems of safety and environmental protection exist, and the industrial popularization of the negative electrode foil is not facilitated.
Disclosure of Invention
The invention aims to provide a solid-state capacitor cathode carbon foil and a preparation method thereof, and a solid-state capacitor and a preparation method thereof.
The invention provides a solid-state capacitor cathode carbon foil which comprises a corrosion aluminum foil and a conducting layer, wherein the conducting layer is coated on the surface of the corrosion aluminum foil, the conducting layer comprises a conducting high polymer layer and a carbon conducting layer, and the conducting high polymer layer is coated on the surface of the corrosion aluminum foil or the surface of the corrosion aluminum foil coated with the carbon conducting layer.
Preferably, the conductive polymer layer comprises a conductive polymer and a binder, and the conductive polymer is at least one of poly (3, 4-ethylenedioxythiophene), poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, polypyrrole-polystyrene sulfonic acid and polystyrene sulfonic acid doped polyaniline; the mass ratio of the conductive high molecular polymer to the binder is 1: 0.5-15.
Preferably, the thickness of the conductive polymer layer is 0.2 to 4 μm.
Preferably, the carbon conducting layer comprises conductive carbon and a binder, and the mass ratio of the conductive carbon to the binder is 1: 0.05-8.
Preferably, the thickness of the carbon conducting layer is 0.5-6 μm.
The invention also provides a preparation method of the solid-state capacitor cathode carbon foil, which comprises the following steps:
coating the conductive high molecular polymer dispersion liquid on the upper surface and the lower surface of a corroded aluminum foil, and drying for the first time to obtain a negative electrode foil of the single-conductive-layer solid-state capacitor;
coating the conductive carbon paste on at least one surface of the single-conductive-layer solid-state capacitor negative electrode foil to enable the conductive carbon paste to completely cover or cover at least one surface of the single-conductive-layer solid-state capacitor negative electrode foil at intervals, and drying for the second time to obtain the solid-state capacitor negative electrode carbon foil;
or the coating sequence of the poly 3, 4-ethylenedioxythiophene dispersion liquid and the conductive carbon slurry is replaced.
The invention also provides a solid-state capacitor, which comprises an anode foil, a diaphragm and a cathode foil, wherein the cathode foil is the solid-state capacitor cathode carbon foil in the technical scheme or the solid-state capacitor cathode carbon foil prepared by the preparation method in the technical scheme; the diaphragm is made of electrolytic paper or non-woven fabric.
The invention also provides a preparation method of the solid-state capacitor in the technical scheme, which comprises the following steps:
(1) stacking the negative electrode foil, the diaphragm and the positive electrode foil, and winding into a core package;
(2) carrying out formation repair on an oxide film of the anode aluminum foil in formation liquid by the core package to obtain a formation core package;
(3) impregnating the formed core cladding with 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate to obtain an impregnated core cladding;
(4) polymerizing the impregnated core package to obtain a capacitor core package;
(5) and assembling and sealing the capacitor core package, the aluminum shell and the rubber plug to obtain the solid capacitor.
Preferably, the molar ratio of the 3, 4-ethylenedioxythiophene to the ferric p-toluenesulfonate is 1: 4-6.
Preferably, the polymerization includes first-order polymerization, second-order polymerization, and third-order polymerization; the temperature of the first-stage polymerization is 30-45 ℃, and the time of the first-stage polymerization is 1-2 h; the temperature of the secondary polymerization is 50-80 ℃, and the time of the secondary polymerization is 1.5-3 h; the temperature of the third-stage polymerization is 130-150 ℃, and the time of the third-stage polymerization is 1-2 h.
The invention provides a solid-state capacitor cathode carbon foil which comprises a corrosion aluminum foil and a conducting layer, wherein the conducting layer is coated on the surface of the corrosion aluminum foil, the conducting layer comprises a conducting high polymer layer and a carbon conducting layer, and the conducting high polymer layer is coated on the surface of the corrosion aluminum foil or the surface of the corrosion aluminum foil coated with the carbon conducting layer. According to the invention, a conductive polymer layer and a carbon conductive layer are coated on a conventional corrosion aluminum foil to obtain the solid-state capacitor cathode carbon foil with a simple structure, the solid-state capacitor cathode carbon foil can be prepared only by a conventional coating method, and the solid-state capacitor prepared by using the cathode foil has the advantages of high capacity, low loss and low ESR value. According to the results of the embodiment, the capacitance of the solid capacitor prepared by using the solid capacitor negative electrode foil provided by the invention is 415-462 muF, which is much higher than that of the comparative example, which is 241-291 muF; the loss is only 4.3-4.9%, which is far lower than the loss of the comparative example by 28-36%; the ESR value is 8.1-8.6 milliohm, which is lower than the ESR value of 21.1-24.2 milliohm of the comparative example; the leakage current for 1 minute is 35 to 62 muA.
Detailed Description
The invention provides a solid-state capacitor cathode carbon foil which comprises a corrosion aluminum foil and a conducting layer, wherein the conducting layer is coated on the surface of the corrosion aluminum foil, the conducting layer comprises a conducting high polymer layer and a carbon conducting layer, and the conducting high polymer layer is coated on the surface of the corrosion aluminum foil or the surface of the corrosion aluminum foil coated with the carbon conducting layer. In the invention, the conductive polymer layer can be more closely attached to the corrosion aluminum foil, so that the loss of the capacitor is reduced; the carbon conductive layer can increase the specific volume of the negative electrode carbon foil.
The position sequence of the conductive high molecular polymer layer and the carbon conductive layer is not specially limited, the conductive high molecular polymer layer can be coated on the surface of the corrosion aluminum foil, the carbon conductive layer is positioned outside the poly 3, 4-ethylenedioxythiophene conductive layer, the carbon conductive layer can also be positioned on the surface of the corrosion aluminum foil, and the conductive high molecular polymer layer is coated on the surface of the corrosion aluminum foil coated with the carbon conductive layer.
The distribution of the carbon conducting layer is not particularly limited, and the distribution of the carbon conducting layer can be adjusted according to the requirement; when the conductive polymer layer is coated on the surface of the corrosion aluminum foil coated with the carbon conductive layer, the carbon conductive layer completely covers or covers at least one surface of the corrosion aluminum foil at intervals; when the conductive polymer layer is coated on the surface of the corrosion aluminum foil, the carbon conductive layer completely covers or covers at least one surface of the corrosion aluminum foil coated with the conductive polymer layer at intervals.
In the present invention, the components of the conductive high molecular polymer layer preferably include a conductive high molecular polymer and a binder.
In the present invention, the conductive high molecular polymer is preferably at least one of poly 3, 4-ethylenedioxythiophene, poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid, polypyrrole-polystyrenesulfonic acid, and polystyrenesulfonic acid-doped polyaniline.
In the present invention, the binder in the conductive polymer layer is preferably an aqueous binder; the aqueous binder is preferably polyvinyl alcohol, polyvinylpyrrolidone, aqueous polyurethane, aqueous epoxy resin or phenolic resin.
In the present invention, the mass ratio of the conductive high molecular polymer to the binder is preferably 1:0.5 to 15, and more preferably 1:2 to 10.
In the present invention, the thickness of the conductive polymer layer is preferably 0.2 to 4 μm, and more preferably 0.5 to 2 μm.
In the present invention, the composition of the carbon conductive layer preferably includes conductive carbon and a binder.
In the present invention, the binder in the carbon conductive layer is preferably polyvinyl alcohol, polyurethane, epoxy resin, phenol resin, or polyvinylidene fluoride.
In the present invention, the conductive carbon is preferably at least one of conductive carbon black, conductive graphite, graphene, and carbon nanotubes.
In the present invention, the mass ratio of the conductive carbon to the binder is preferably 1:0.05 to 8, more preferably 1:0.1 to 3, and most preferably 1:0.5 to 0.8.
In the invention, the thickness of the etched aluminum foil is preferably 30-125 μm, and more preferably 40-65 μm.
The invention also provides a preparation method of the solid-state capacitor cathode carbon foil, which comprises the following steps:
coating the conductive high molecular polymer dispersion liquid on the upper surface and the lower surface of a corroded aluminum foil, and drying for the first time to obtain a negative electrode foil of the single-conductive-layer solid-state capacitor;
coating the conductive carbon paste on at least one surface of the single-conductive-layer solid-state capacitor negative electrode foil to enable the conductive carbon paste to completely cover or cover at least one surface of the single-conductive-layer solid-state capacitor negative electrode foil at intervals, and drying for the second time to obtain the solid-state capacitor negative electrode carbon foil;
or the coating sequence of the poly 3, 4-ethylenedioxythiophene dispersion liquid and the conductive carbon slurry is replaced.
In the invention, the specific volume of the corroded aluminum foil is preferably more than or equal to 200 mu F/cm2. The source of the corrosion aluminum foil is not particularly limited, and the corrosion aluminum foil sold in the market can be adopted. In the embodiment of the invention, the corrosion aluminum foil is preferably a corrosion aluminum foil with the model number of F545 manufactured by the crown industry company.
In the present invention, the conductive high molecular polymer dispersion liquid preferably includes a conductive high molecular polymer, a binder, and water.
In the present invention, the concentration of the conductive polymer in the conductive polymer dispersion is preferably 0.5 to 10 wt.%, and more preferably 1 to 5 wt.%.
In the present invention, the concentration of the binder in the conductive polymer dispersion is preferably 0.5 to 15 wt.%, and more preferably 1 to 10 wt.%.
In the present invention, the binder in the conductive polymer dispersion is preferably an aqueous binder; the aqueous binder is preferably polyvinyl alcohol, polyvinylpyrrolidone, aqueous polyurethane, aqueous epoxy resin or phenolic resin.
In the present invention, the source of the conductive polymer dispersion is not particularly limited, and a commercially available conductive polymer dispersion may be prepared or used.
In the present invention, the coating surface density of the conductive polymer dispersion is preferably 0.5 to 30g/m2More preferably 5 to 25g/m2Most preferably 13 to 22g/m2。
In the present invention, the conductive carbon paste preferably includes conductive carbon, a binder, and a solvent.
In the present invention, the solvent is preferably water or an organic solvent; the organic solvent is preferably ethanol or N-methylpyrrolidone.
In the present invention, the concentration of the conductive carbon in the conductive carbon paste is preferably 1 to 10 wt.%, more preferably 3 to 7 wt.%, and most preferably 4 to 6 wt.%.
In the invention, the concentration of the binder in the conductive carbon paste is preferably 0.5-8 wt.%, more preferably 1-7 wt.%, and most preferably 3-5 wt.%.
In the present invention, when the solvent is water, the binder in the conductive carbon paste is preferably an aqueous binder; the aqueous binder is preferably polyvinyl alcohol, aqueous polyurethane, aqueous epoxy resin or phenolic resin. In the present invention, when the solvent is an organic solvent, the binder in the conductive carbon paste is preferably a nonaqueous binder, and the nonaqueous binder is preferably polyvinylidene fluoride or epoxy resin.
In the present invention, the conductive carbon is preferably at least one of conductive carbon black, conductive graphite, graphene, and carbon nanotubes.
In the invention, the coating surface density of the conductive carbon paste is preferably 1-50 g/m2More preferably 5 to 30g/m2Most preferably 10 to 15g/m2。
The invention has no special limitation on the coating mode of the conductive high molecular polymer dispersion liquid and the conductive carbon slurry, and can obtain a uniform conductive layer. In the present invention, the coating is preferably gravure coating, knife coating, printing, spray coating or printing.
The drying modes and specific parameters of the first drying and the second drying are not particularly limited, and a product with constant weight can be obtained.
The invention also provides a solid-state capacitor, which comprises an anode foil, a diaphragm and a cathode foil, wherein the cathode foil is the solid-state capacitor cathode carbon foil in the technical scheme or the solid-state capacitor cathode carbon foil prepared by the preparation method; the diaphragm is made of electrolytic paper or non-woven fabric.
The invention also provides a preparation method of the solid-state capacitor in the technical scheme, which comprises the following steps:
(1) laminating the negative foil, the diaphragm and the positive aluminum foil, and winding into a core package;
(2) carrying out formation repair on an oxide film of the anode aluminum foil in formation liquid by the core package to obtain a formation core package;
(3) impregnating the formed core cladding with 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate to obtain an impregnated core cladding;
(4) polymerizing the impregnated core package to obtain a capacitor core package;
(5) and assembling and sealing the capacitor core package, the aluminum shell and the rubber plug to obtain the solid capacitor.
The invention stacks the negative foil, the electrolytic paper and the positive aluminum foil in sequence and winds the stacked foils into a core bag.
The source of the positive aluminum foil is not particularly limited, and a commercially available positive aluminum foil can be used. In the embodiment of the invention, the positive aluminum foil is preferably positive foil forming voltage of 10V and specific volume of 230 mu F/cm of JCC company of Japan2The positive electrode aluminum foil of (1).
The winding method of the present invention is not particularly limited, and a winding method that is conventional in the art may be used. In the embodiment of the invention, the stacking sequence is from bottom to top, the diaphragm, the negative electrode foil, the diaphragm and the positive electrode foil are sequentially arranged, and the diaphragm, the negative electrode foil, the diaphragm and the positive electrode foil are wound into a cylinder from one end during winding; the two layers of the diaphragm are preferably independent electrolytic paper or non-woven fabric.
The sizes of the negative electrode foil, the positive electrode aluminum foil, the electrolytic paper and the core package are not particularly limited, and can be adjusted by a person skilled in the art according to needs. In the present embodiment, the core package preferably has a size of 6.3mm in diameter and 5mm in height.
After the core package is obtained, the core package is subjected to chemical conversion repair on the oxide film of the anode aluminum foil in chemical conversion liquid to obtain the chemical core package. Usually, a layer of oxide film exists on the surface of the positive aluminum foil, and in the operation process, the oxide film on the surface of the positive aluminum foil can generate defects, and aluminum exposed at the defects can be repaired into aluminum oxide through repair, so that the leakage current of the product is reduced.
In the present invention, the chemical solution is preferably an aqueous ammonium adipate solution, an aqueous phosphate solution, or an aqueous ammonium sebacate solution, and more preferably an aqueous ammonium adipate solution. In the present invention, when the chemical solution is an ammonium adipate aqueous solution, the mass concentration of the ammonium adipate aqueous solution is preferably 6 to 10 wt.%, and more preferably 8 wt.%.
In the invention, the voltage of the formation repair is preferably 5-15V, more preferably 7-12V, and most preferably 9-10V; the temperature of the formation repair is preferably 35-55 ℃, and more preferably 40-50 ℃; the time for the formation repair is preferably 30-50 min, and more preferably 35-45 min.
After the formation repair is finished, the invention preferably sequentially cleans and dries the product obtained by the formation repair to obtain the formation core package.
The cleaning mode is not particularly limited in the invention, and the conventional cleaning mode in the field can be adopted. The drying mode is not particularly limited, and the moisture in the core bag can be completely removed.
After the formation core package is obtained, the formation core package is impregnated with 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate to obtain the impregnated core package. In the invention, the 3, 4-ethylenedioxythiophene is a monomer, the ferric p-toluenesulfonate is used as an oxidant, and the formed core packet is impregnated with the two substances to prepare for the subsequent polymerization reaction.
In the invention, the molar ratio of the 3, 4-ethylenedioxythiophene to the ferric p-toluenesulfonate is preferably 1: 4-6, and more preferably 1: 5.
In the present invention, it is preferable that the 3, 4-ethylenedioxythiophene and the iron p-toluenesulfonate are impregnated at the same time or separately with the 3, 4-ethylenedioxythiophene and the iron p-toluenesulfonate.
In the present invention, when the impregnation is simultaneous impregnation of 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate, the impregnation is preferably to impregnate the formation core package in a mixed solution containing 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate; the solvent of the mixed solution is preferably methanol, ethanol or n-butanol; the concentration of the iron p-toluenesulfonate in the mixed solution is preferably 50 to 75 wt.%, more preferably 55 to 70 wt.%, and most preferably 60 to 65 wt.%; the impregnation temperature is preferably room temperature; the impregnation time is preferably 1 to 20min, more preferably 2 to 15min, and most preferably 3 to 10 min.
In the present invention, when the impregnation is performed by respectively impregnating 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate, the order of impregnating 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate is not particularly limited in the present invention, and 3, 4-ethylenedioxythiophene may be impregnated first and then ferric p-toluenesulfonate may be impregnated first, or ferric p-toluenesulfonate may be impregnated first and then 3, 4-ethylenedioxythiophene.
In the present invention, the impregnation of 3, 4-ethylenedioxythiophene is preferably performed by immersing the formed core package or the formed core package impregnated with iron p-toluenesulfonate in a 3, 4-ethylenedioxythiophene solution; the solvent of the 3, 4-ethylenedioxythiophene solution is preferably methanol, ethanol or n-butanol; the concentration of the 3, 4-ethylenedioxythiophene solution is preferably 20-40 wt.%, and more preferably 25-30 wt.%; the temperature for impregnating the 3, 4-ethylenedioxythiophene is preferably room temperature; the impregnation time of the 3, 4-ethylenedioxythiophene is preferably 1-20 min, more preferably 2-15 min, and most preferably 3-10 min.
In the present invention, the impregnation of iron p-toluenesulfonate is preferably performed by immersing the formed core packet or the formed core packet impregnated with 3, 4-ethylenedioxythiophene in an iron p-toluenesulfonate solution; the solvent of the iron p-toluenesulfonate solution is preferably methanol, ethanol or n-butanol; the concentration of the iron p-toluenesulfonate solution is preferably 40 to 75 wt.%, more preferably 45 to 70 wt.%, and most preferably 50 to 60 wt.%; the temperature for impregnating the iron p-toluenesulfonate is preferably room temperature; the time for impregnating the iron p-toluenesulfonate is preferably 1 to 20min, more preferably 2 to 15min, and most preferably 3 to 10 min.
After obtaining the impregnated core package, the impregnated core package is preferably polymerized to obtain the capacitor core package. In the invention, 3, 4-ethylenedioxythiophene is polymerized into a poly 3, 4-ethylenedioxythiophene high-molecular conductive substance through polymerization, so that the Equivalent Series Resistance (ESR) value is reduced.
In the present invention, the polymerization preferably includes first-order polymerization, second-order polymerization, and third-order polymerization; the temperature of the first-stage polymerization is preferably 30-45 ℃, and more preferably 35-40 ℃; the time of the primary polymerization is preferably 1-2 h; the temperature of the secondary polymerization is preferably 50-80 ℃, and more preferably 60-70 ℃; the secondary polymerization time is preferably 1.5-3 h, and more preferably 2-2.5 h; the temperature of the three-stage polymerization is preferably 130-150 ℃, and more preferably 135-145 ℃; the time of the three-stage polymerization is preferably 1-2 h; the heating rate of the temperature of the first-stage polymerization to the temperature required by the second-stage polymerization is not particularly limited and can be any rate; the temperature rise rate of the temperature of the second-stage polymerization to the temperature required by the third-stage polymerization is not particularly limited, and can be any temperature rise rate.
In the invention, the 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate undergo a chemical reaction at a low temperature in the primary polymerization process to obtain a low Equivalent Series Resistance (ESR) value; the secondary polymerization process is carried out at a higher temperature, so that the reaction speed is increased, the monomers are fully polymerized to form more conductive polymers, the ESR value is further reduced, the temperature is too low, the reaction speed is slow, the time is long, the improvement of the production efficiency is not facilitated, the temperature is too high, the ESR value is large, and defective products are increased; the tertiary polymerization process further raises the reaction temperature to complete the reaction and completely volatilizes the solvent.
After polymerization is finished, the core package of the capacitor, the aluminum shell and the rubber plug are assembled and sealed to obtain the solid capacitor.
The invention has no special limitation on the assembling and sealing mode, and the assembling and sealing mode which is conventional in the field can be adopted.
In the present invention, the solid state capacitor is preferably aged before use. The product leakage current can be reduced by aging.
In the present invention, the aging preferably includes primary aging and secondary aging; the voltage of the primary aging is preferably 3-5V, and more preferably 4-4.5V; the first-stage aging time is preferably 20-40 min, and more preferably 25-30 min; the voltage of the secondary aging is preferably 6-8V, and more preferably 6.3-7V; the first-stage aging time is preferably 20-40 min, and more preferably 25-30 min; the temperature of the primary aging and the temperature of the secondary aging are independent and preferably 115-135 ℃, and more preferably 120-130 ℃.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
(1) Specific volume is 450 mu F/cm2And a corrosion aluminum foil with the thickness of 50 mu m is taken as a negative electrode foil substrate, and the surface of the negative electrode foil substrate is coated with poly 3, 4-ethylenedioxythiophene dispersion liquid by adopting a gravure coating technology, wherein the coating density is 30g/m2Drying at 85 ℃ to obtain a negative foil with the surface coated with the poly 3, 4-ethylenedioxythiophene conductive layer; the poly 3, 4-ethylenedioxythiophene dispersion liquid is prepared by self, wherein the concentration of the poly 3, 4-ethylenedioxythiophene is 0.5 wt.%, the binder is polyvinyl alcohol, and the concentration is 3 wt.%; the thickness of the poly 3, 4-ethylenedioxythiophene conducting layer is 2 microns;
(2) coating a layer of conductive graphene slurry on the surface of a negative electrode foil coated with a poly (3, 4-ethylenedioxythiophene) conductive layer on the surface by adopting a gravure coating technology, wherein the coating density is 25g/m2Drying at 100 ℃ to obtain the capacitor negative electrode foil coated with the poly 3, 4-ethylenedioxythiophene conductive layer and the carbon conductive layer; the conductive graphene slurry comprises 2 wt.% of graphene, 1 wt.% of polyurethane and the balance of water; the thickness of the carbon conducting layer of the obtained capacitor negative electrode foil is 2 mu m;
(3) the formation voltage is 10V, the specific volume is 230 mu F/cm2The positive aluminum foil and the negative foil of the capacitor are respectively cut to be 4mm wide, and then are laminated with electrolytic paper with the paper width of 5mm, the electrolytic paper is positioned between the positive aluminum foil and the negative aluminum foil, and the laminated positive aluminum foil, the laminated electrolytic paper and the laminated negative aluminum foil are wound into a core bag with the size of 6.3 x 5 mm; positive foil winding length 76 MM;
(3) putting the capacitor core package into 8 wt.% ammonium adipate water solution at the temperature of 40 ℃, applying a direct-current voltage of 9V, and performing formation repair for 40 min; after the formation repair is completed, cleaning the obtained core package with pure water, and drying to obtain a formation core package;
(4) soaking the formed core package in a mixed solution of 62 wt.% of ferric p-toluenesulfonate ethanol solution and 3, 4-ethylenedioxythiophene for 5 minutes to obtain an impregnated core package; the mass ratio of the ferric p-toluenesulfonate to the 3, 4-ethylenedioxythiophene is 5:1,
(5) polymerizing the impregnated core package at 40 ℃ for 1h, then heating to 60 ℃ for polymerizing for 2h, and then heating to 150 ℃ for polymerizing for 1h to obtain a capacitor core package;
(6) and assembling and sealing the capacitor core package, the aluminum shell and the rubber plug to obtain the solid capacitor.
And 4 solid capacitors prepared in the batch are selected, and the electrical property of the capacitors is tested after aging. The specific aging steps are as follows: the solid state capacitor was aged at 125 deg.C for 30min at 4V and then 30min at 6.3V.
The solid state capacitor was tested for capacitance and loss at 120Hz, leakage current at 6.3V for 1min, and ESR at 100KHZ using the methods set forth in the national standard GB5995-86, and the results are shown in Table 1.
Example 2
(1) Specific volume is 450 mu F/cm2And a corrosion aluminum foil with the thickness of 50 mu m is taken as a negative electrode foil substrate, the surface of the negative electrode foil substrate is coated with poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid dispersion liquid by adopting a gravure coating technology, and the coating density is 10g/m2Drying at 85 ℃ to obtain a negative electrode foil with the surface coated with a poly (3, 4-ethylenedioxythiophene) -poly (3, 4-ethylenedioxythiophene styrene sulfonic acid) conducting layer; the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid dispersion is a model 1802007 dispersion produced by Bohong corporation; wherein the concentration of poly 3, 4-ethylenedioxythiophene is 1.5 wt.%, wherein the binder is polyvinylpyrrolidone and the concentration is 5 wt.%, and the thickness of the poly 3, 4-ethylenedioxythiophene-polystyrenesulfonic acid conductive layer is 0.6 μm;
(2) coating a layer of conductive graphene slurry on the surface of a negative electrode foil coated with a poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid conductive layer on the surface by adopting a gravure coating technology, wherein the coating density is 10g/m2Drying at 100 ℃ to obtain the conductive layer coated with poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid and the carbon conductorA capacitor negative foil of the electrical layer; the conductive graphene slurry comprises 2 wt.% of graphene, 1 wt.% of polyurethane and the balance of water; the thickness of the carbon conducting layer of the obtained capacitor negative electrode foil is 0.8 mu m;
(3) the formation voltage is 10V, the specific volume is 230 mu F/cm2The positive aluminum foil and the negative foil of the capacitor are respectively cut to be 4mm wide, and then are laminated with electrolytic paper with the paper width of 5mm, the electrolytic paper is positioned between the positive aluminum foil and the negative aluminum foil, and the laminated positive aluminum foil, the laminated electrolytic paper and the laminated negative aluminum foil are wound into a core bag with the size of 6.3 x 5 mm; positive foil winding length 76 MM;
(3) putting the capacitor core package into 8 wt.% ammonium adipate water solution at the temperature of 40 ℃, applying a direct-current voltage of 9V, and performing formation repair for 40 min; after the formation repair is completed, cleaning the obtained core package with pure water, and drying to obtain a formation core package;
(4) soaking the formed core package in a mixed solution of 62 wt.% of ferric p-toluenesulfonate ethanol solution and 3, 4-ethylenedioxythiophene for 5 minutes to obtain an impregnated core package; the mass ratio of the ferric p-toluenesulfonate to the 3, 4-ethylenedioxythiophene is 5:1,
(5) polymerizing the impregnated core package at 40 ℃ for 1h, then heating to 60 ℃ for polymerizing for 2h, and then heating to 150 ℃ for polymerizing for 1h to obtain a capacitor core package;
(6) and assembling and sealing the capacitor core package, the aluminum shell and the rubber plug to obtain the solid capacitor.
And 3 solid capacitors prepared in the batch are selected, and the electrical property of the capacitors is tested after aging. The specific aging steps are as follows: the solid state capacitor was aged at 125 deg.C for 30min at 4V and then 30min at 6.3V.
The solid state capacitor was tested for capacitance and loss at 120Hz, leakage current at 6.3V for 1min, and ESR at 100KHZ using the methods set forth in the national standard GB5995-86, and the results are shown in Table 1.
Comparative example 1
The negative electrode foil substrate used in example 1 was used as a negative electrode foil (without coating the poly 3, 4-ethylenedioxythiophene dispersion and the carbon conductive layer) and the formation voltage was used as10V and a specific volume of 230 mu F/cm2The same procedure as in example 1 was repeated except that the positive electrode aluminum foil of (1) was used as a positive electrode foil to prepare a solid state capacitor.
4 of the batch of solid state capacitors were selected and tested for electrical performance according to the aging and electrical performance test method described in example 1, with the results shown in table 1.
As can be seen from Table 1, the capacitance of the solid-state capacitor provided by the invention is 415-462 muF, which is far superior to that of the capacitor of comparative example 1, which is 241-291 muF; the loss is only 4.3-4.9%, which is far lower than the loss of the comparative example by 28-36%; the ESR value is 8.1-8.6 milliohm, which is lower than the ESR value of 21.1-24.2 milliohm of the comparative example; the leakage current for 1 minute is 35 to 62 muA. Therefore, the poly 3, 4-ethylenedioxythiophene conducting layer is coated on the negative aluminum foil and then used for preparing the solid capacitor, and the electrical property of the solid capacitor is obviously improved.
Table 1 results of electrical property test of solid state capacitors obtained in example 1 and comparative example 1
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A solid capacitor comprises a positive foil, a diaphragm and a negative foil, wherein the negative foil comprises a corrosion aluminum foil and a conductive layer, the conductive layer is coated on the surface of the corrosion aluminum foil, the conductive layer comprises a conductive high polymer layer and a carbon conductive layer, and the conductive high polymer layer is coated on the surface of the corrosion aluminum foil or the surface of the corrosion aluminum foil coated with the carbon conductive layer; the diaphragm is electrolytic paper or non-woven fabric;
the preparation method of the solid-state capacitor cathode carbon foil comprises the following steps:
coating the conductive high molecular polymer dispersion liquid on the upper surface and the lower surface of a corroded aluminum foil, and drying for the first time to obtain a negative electrode foil of the single-conductive-layer solid-state capacitor;
coating the conductive carbon paste on at least one surface of the single-conductive-layer solid-state capacitor negative electrode foil to enable the conductive carbon paste to completely cover or cover at least one surface of the single-conductive-layer solid-state capacitor negative electrode foil at intervals, and drying for the second time to obtain the solid-state capacitor negative electrode carbon foil; the conductive carbon slurry consists of conductive carbon, a binder and a solvent;
or the coating sequence of the conductive high molecular polymer dispersion liquid and the conductive carbon slurry is replaced;
the preparation method of the solid capacitor comprises the following steps:
(1) stacking the negative electrode foil, the diaphragm and the positive electrode foil, and winding into a core package;
(2) carrying out formation repair on an oxide film of the anode aluminum foil in formation liquid by the core package to obtain a formation core package;
(3) impregnating the formed core cladding with 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate to obtain an impregnated core cladding;
(4) polymerizing the impregnated core package to obtain a capacitor core package;
(5) and assembling and sealing the capacitor core package, the aluminum shell and the rubber plug to obtain the solid capacitor.
2. A solid state capacitor according to claim 1, wherein the conductive polymer layer comprises a conductive polymer and a binder, the conductive polymer being at least one of poly 3, 4-ethylenedioxythiophene, poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, polypyrrole-polystyrene sulfonic acid and polystyrene sulfonic acid doped polyaniline; the mass ratio of the conductive high molecular polymer to the binder is 1: 0.5-15.
3. A solid state capacitor as claimed in claim 1 or 2, wherein the conductive polymer layer has a thickness of 0.2 to 4 μm.
4. The solid-state capacitor according to claim 1, wherein the composition of the carbon conductive layer comprises conductive carbon and a binder, and the mass ratio of the conductive carbon to the binder is 1: 0.05-8.
5. A solid state capacitor as claimed in claim 1 or 4, wherein the carbon conductive layer has a thickness of 0.5 to 6 μm.
6. A method of manufacturing a solid state capacitor as claimed in any one of claims 1 to 5, comprising the steps of:
(1) stacking the negative electrode foil, the diaphragm and the positive electrode foil, and winding into a core package;
(2) carrying out formation repair on an oxide film of the anode aluminum foil in formation liquid by the core package to obtain a formation core package;
(3) impregnating the formed core cladding with 3, 4-ethylenedioxythiophene and ferric p-toluenesulfonate to obtain an impregnated core cladding;
(4) polymerizing the impregnated core package to obtain a capacitor core package;
(5) and assembling and sealing the capacitor core package, the aluminum shell and the rubber plug to obtain the solid capacitor.
7. The preparation method according to claim 6, wherein the molar ratio of the 3, 4-ethylenedioxythiophene to the iron p-toluenesulfonate is 1: 4-6.
8. The production method according to claim 6, wherein the polymerization includes a primary polymerization, a secondary polymerization, and a tertiary polymerization; the temperature of the first-stage polymerization is 30-45 ℃, and the time of the first-stage polymerization is 1-2 h; the temperature of the secondary polymerization is 50-80 ℃, and the time of the secondary polymerization is 1.5-3 h; the temperature of the third-stage polymerization is 130-150 ℃, and the time of the third-stage polymerization is 1-2 h.
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| CN105405657A (en) * | 2014-09-16 | 2016-03-16 | 立隆电子工业股份有限公司 | Electrolytic capacitor manufacturing method and product thereby |
| CN107275092A (en) * | 2017-07-08 | 2017-10-20 | 全椒金富康电子有限公司 | A kind of capacitor core bag and preparation method thereof and a kind of solid aluminum electrolytic capacitor |
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| CN102426924A (en) * | 2011-10-13 | 2012-04-25 | 李荐 | High-performance aluminum/carbon composite electrode foil and preparation method thereof |
| CN102832392A (en) * | 2012-06-27 | 2012-12-19 | 长沙业翔能源科技有限公司 | Current collector carbon coated aluminum foil and its preparation method |
| CN105405657A (en) * | 2014-09-16 | 2016-03-16 | 立隆电子工业股份有限公司 | Electrolytic capacitor manufacturing method and product thereby |
| CN107275092A (en) * | 2017-07-08 | 2017-10-20 | 全椒金富康电子有限公司 | A kind of capacitor core bag and preparation method thereof and a kind of solid aluminum electrolytic capacitor |
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