CN105761937B - A kind of aluminum electrolytic condenser and preparation method thereof - Google Patents
A kind of aluminum electrolytic condenser and preparation method thereof Download PDFInfo
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- CN105761937B CN105761937B CN201610101656.1A CN201610101656A CN105761937B CN 105761937 B CN105761937 B CN 105761937B CN 201610101656 A CN201610101656 A CN 201610101656A CN 105761937 B CN105761937 B CN 105761937B
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 61
- 239000002322 conducting polymer Substances 0.000 claims abstract description 29
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 230000005611 electricity Effects 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 150000001450 anions Chemical class 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 13
- 230000003252 repetitive effect Effects 0.000 claims description 9
- 239000003990 capacitor Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229920000767 polyaniline Polymers 0.000 claims description 6
- 229920000123 polythiophene Polymers 0.000 claims description 6
- -1 sulfonic acids anion Chemical class 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 5
- 150000005846 sugar alcohols Chemical class 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 150000002240 furans Chemical class 0.000 claims description 3
- 150000002596 lactones Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000003951 lactams Chemical group 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 description 18
- 239000000203 mixture Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 229920000447 polyanionic polymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920001088 polycarbazole Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
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
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
-
- 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
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention relates to a kind of aluminum electrolytic condenser, the oxidation voltage of the anode of the aluminum electrolytic condenser is greater than 30V, including dispersion, and the dispersion includes conducting polymer and dispersing agent, and the average grain diameter of the conducting polymer is 10-30nm.The invention further relates to a kind of preparation methods of aluminum electrolytic condenser.Aluminum electrolytic condenser of the invention has the advantages that be easy, it is low that low, equivalent series resistance is lost and leaks electricity low.
Description
Technical field
The present invention relates to capacitor technology, in particular to a kind of aluminum electrolytic condenser and preparation method thereof.
Background technique
Conducting polymer is a kind of high-molecular compound with conjugatedπbond structure, by chemistry or electrochemical doping pair
Anion or to the conductive special high molecular material formed after cation, including polyacetylene, polythiophene, polypyrrole,
Polyaniline gathers to benzene, polycarbazole and polyfluorene etc..The outstanding advantages of conducting polymer are light both with metal and semiconductor material
Electrical characteristics, and there is the good stability of polymer and mechanical property, quality is relatively light, and is easily worked.Industry at present
Field is using poly- (3, the 4- second that most successful conducting polymer is among polyaniline and polythiophene, especially polythiofuran derivative
Support dioxy thiophene) (PEDOT), even more because of its high conductivity, good environmental stability, dopant states when it is transparent the advantages that, and
It shows in organic electroluminescence, obtain broad commercial applications in the electronic devices such as organic solar batteries and supercapacitor.
Since self-conductive macromolecule is found, either the product that is prepared of electrochemical method or chemical method is generally all
It is the conducting polymer powder of slightly solubility, it is difficult to process, therefore greatly limit their application.Until the Bayer eighties in last century
Company introduces poly- p styrene sulfonic acid (PSS) conduct during the chemical oxidising polymerisation of 3,4-ethylene dioxythiophene (EDOT)
Charge balance dopant prepares poly- (3,4-ethylene dioxythiophene)/poly- p styrene sulfonic acid (PEDOT/PSS), with excellent
Good water dispersion, coating film forming performance, high conduction performance, optical transparence, environmental stability etc. have been applied to super at present
The fields such as grade capacitor, antistatic coating, corrosion-inhibiting coating, electroluminescent material, sensor, electrically conductive ink.
The Chinese invention patent of Patent No. 200680033112.0 discloses a kind of preparation method of electrolytic condenser,
The method at least includes the following steps: a) making the porous electrode body (2) of electrode material through anodic oxidation reactions to form covering
The dielectric (3) of the electrode material surface;B) apply dispersion A in porous bodies), the porous bodies include at least electrode
The porous electrode body (2) and dielectric (3) of material, the dispersion A) including at least the particle B of conducting polymer) and dispersing agent
D);C) it is the solid electrolyte (4) for forming complete or partial covering dielectric surface, at least partly removes and/or solidify and divide
Powder D), maximum anodizing voltage of the porous electrode body (2) during anodic oxidation is greater than conducting polymer in 30V, dispersion A)
Composition granule B) average grain diameter be 1-100nm.That is: applying conductive particle average grain diameter is 1-100nm, and anodic oxidation voltage is greater than
30V.It finds after tested, electrolytic condenser described in foregoing invention still has can be with loss, equivalent series electricity in capacitive out
The problem of resistance, electric leakage performance cannot be considered in terms of
Summary of the invention
The technical problems to be solved by the present invention are: providing one kind can control suitable molecular weight, be easy with using appearance,
The aluminum electrolytic condenser that low, equivalent series resistance is low and electric leakage is low is lost, it is further provided above-mentioned aluminum electrolytic condenser
Preparation method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
A kind of aluminum electrolytic condenser, the oxidation voltage of the anode of the aluminum electrolytic condenser are greater than 30V, including dispersion
Body, the dispersion include conducting polymer and dispersing agent, and the average grain diameter of the conducting polymer is 10-30nm.
The present invention also provides a kind of preparation methods of aluminum electrolytic condenser, in the electrode of above-mentioned aluminum electrolytic condenser
It is upper to apply the dispersion, then the dispersing agent is partly or entirely removed, or the dispersing agent is solidified, it is described
Removal or cured number be once or twice more than.
The beneficial effects of the present invention are:
(1) when the oxidation voltage of anode is greater than 30V, when aperture is larger, the average grain diameter for controlling conducting polymer is 10-
The design of 30nm reaches and holds easy technical effect out;
(2) aluminum electrolytic condenser obtained has the advantages that loss is low, equivalent series resistance is low and electric leakage is low.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained below in conjunction with embodiment.
The most critical design of the present invention is: under conditions of anodic oxidation voltage is greater than 30V, by controlling conducting polymer
The average grain diameter of object is 10-30nm, holds easy technical effect out to reach.
The present invention provides a kind of aluminum electrolytic condenser, and the oxidation voltage of the anode of the aluminum electrolytic condenser is greater than
30V, including dispersion, the dispersion include conducting polymer and dispersing agent, and the average grain diameter of the conducting polymer is 10-
30nm。
The present invention also provides a kind of preparation methods of aluminum electrolytic condenser, in the electrode of above-mentioned aluminum electrolytic condenser
It is upper to apply the dispersion, then the dispersing agent is partly or entirely removed, or the dispersing agent is solidified, it is described
Removal or cured number be once or twice more than.
Technical concept of the invention are as follows:
The relationship of known capacitor voltage and the energy of capacitive out are as follows: with the raising of voltage, the aperture of porous anode becomes larger, electricity
Pressure is lower, and aperture is smaller, and holding will be more difficult to out.
When molecular weight is smaller, then partial size is smaller, and still, stability, electric conductivity can be deteriorated, thus when partial size is 1-
10nm can keep dispersion bulk conductivity low, the capacitor equivalent series resistance prepared can become larger because partial size is too small;Work as molecule
Amount is big, then partial size is big, and stability can be got well, and electric conductivity is more excellent, and still, molecular weight is excessive, partial size again can too greatly, be unfavorable for into
Enter in the hole of porous anode;Thus when partial size is 30-100nm, meeting be unfavorable for dispersion and enter electrode because partial size is too big
Kong Zhong, the capacitor prepared go out that capacity rate is low and loss is high.Therefore, electrolytic condenser in the prior art, which exists, to hold
The problem of rate, drain performance and equivalent series resistance, electric conductivity (such as electric leakage performance) cannot be taken into account.
And the applicant is based on the discovery of the above problem, when the oxidation voltage of anode is greater than 30V, control is led for discovery
Electric grain diameter is between 10-30nm, the shearing of PEDOT/PSS dispersion liquid, the partial size and polystyrolsulfon acid (pss) after homogeneous
Molecular weight is in close relations;Comprehensively consider the stability, electric conductivity and partial size of dispersion liquid, and obtained by long-term experiment: in sun
The oxidation voltage of pole is greater than 30V, and the average grain diameter for controlling conducting polymer is 10-30nm, at this time its aperture and grain under the voltage
The cooperation of diameter can achieve out the high technical effect of capacity rate;Meanwhile the aperture when voltage is greater than 30V is larger, dispersion is easy
It enters in hole, the dispersion entered in hole is more, and the capacitor performance made is better, therefore the aluminum electrolytic condenser obtained
Have the advantages that loss is low, equivalent series resistance is low and electric leakage is low.
As can be seen from the above description, the beneficial effects of the present invention are:
(1) when the oxidation voltage of anode is greater than 30V, when aperture is larger, the average grain diameter for controlling conducting polymer is 10-
The design of 30nm reaches and holds easy technical effect out;
(2) aluminum electrolytic condenser obtained has the advantages that loss is low, equivalent series resistance is low and electric leakage is low.
Further, the conducting polymer includes polythiofuran derivative, and the polythiofuran derivative includes with following
The repetitive unit of general formula I and/or general formula II composition, the structural formula of the general formula I are as follows:
The structural formula of the general formula II are as follows:
In the structural formula of the general formula I and the structural formula of general formula II, A is the alkylene that the carbon atom number optionally replaced is 1-5
Base;R be the carbon atom number optionally replaced be 5-12 direct-connected or branch naphthenic base, the carbon atom number that optionally replaces be the straight of 6-14
Chain or branch aryl, the linear chain or branched chain aralkyl that the carbon atom number optionally replaced is 7-18, the carbon atom number optionally replaced are
The linear chain or branched chain hydroxyalkyl or hydroxyl of 1-4;X is the integer of 0-8.
In the case where A is combined with several A groups, these groups can be identical or different.
The polythiofuran derivative of the invention can be the repetitive unit formed with general formula I, or have logical
The repetitive unit of Formula II composition can also be the repetitive unit with general formula I and general formula II composition.
Seen from the above description, polythiofuran derivative can be optionally substituted polythiophene, and preferably above-mentioned includes tool
The repetitive unit being made of the following general formula I and/or general formula II.The polythiofuran derivative of above structure can preferably and anode hole
Diameter size is cooperated, and the easy degree held is further increased out.
Further, the conducting polymer further includes at least one of Polypyrrole derivatives and polyaniline derivative.
Further, the dispersion further includes polymeric anion.Preferably, the polymeric anion is polymerization of carboxylic acid yin
Ion or sulfonic acids anion.More preferably, the polymeric anion is polystyrolsulfon acid anion, the polyphenyl second
The molecular weight of alkene sulfonic acid anion is 2000-500000.
Seen from the above description, polymeric anion is added in dispersion, polyanion can do compound ion, with polythiophene
Compound to be subsequently dispersed in water, polyanion can also be used as dopant simultaneously, control the molecule of polystyrolsulfon acid anion
Amount is 2000-500000, polythiophene can be made preferably to be dispersed in water.Wherein, more preferably, polystyrolsulfon acid yin from
The molecular weight of son is 10000-200000.
Further, the dispersing agent is organic solvent and/or water.
Further, the dispersion further includes at least one of crosslinking agent, surfactant and additive, described to add
Agent is added to be selected from ether, lactone, amide group, lactams group, sulfone, sulfoxide, sugar, sugar derivatives, sugar alcohol, furan derivatives, binary
At least one of pure and mild polyalcohol.
Seen from the above description, the crosslinking agent and surfactant can using common crosslinking agent in the prior art and
Surfactant.The effect that crosslinking agent, surfactant and additive are respectively provided with effectively crosslinking, reduce surface tension is added.
Further, the pH value of the dispersion is 1.5-7, and the viscosity of the dispersion at 20 °C is not more than
500cps。
Seen from the above description, can pH value to dispersion and viscosity carry out above-mentioned control, more preferably, dispersion
PH value be 2-5, while its viscosity can be tested under the revolving speed of 60rpm.
In the preparation method of aluminum electrolytic condenser of the invention:
Acid or alkali can be added to adjust in pH value in dispersion;It is described " to apply the dispersion, then by the dispersing agent
The step of partly or entirely removal, or the dispersing agent is solidified ", can carry out primary or be repeated twice above.
In addition, the screening of the composition of the design and dispersion base of the synthesis of dispersion liquid of the invention, can fully consider
Stability, electric conductivity and the partial size of dispersion liquid, with obtain good property (be easy out, be lost low, equivalent series resistance it is low with
And electric leakage is low).
The embodiment of the present invention one are as follows:
A kind of aluminum electrolytic condenser of the present embodiment, the oxidation voltage of the anode of the aluminum electrolytic condenser are 30V,
Including dispersion, it further includes additive that the dispersion, which includes conducting polymer, dispersing agent and polymeric anion, the addition
Agent is the mixture of ether, lactone, amide group, furan derivatives and polyalcohol.The pH value of the dispersion be 1.5, described point
The viscosity of granular media at 20 °C is 500cps.The average grain diameter of the conducting polymer is 10nm.The conducting polymer
It further include Polypyrrole derivatives including polythiofuran derivative.The polymeric anion is polystyrolsulfon acid anion, described poly-
The molecular weight of styrene sulfonic acid anion is 2000, and the dispersing agent is water.The polythiofuran derivative includes having following lead to
The repetitive unit of Formulas I composition, the structural formula of the general formula I are as follows:
In the structural formula of the general formula I, A is the alkylidene that the carbon atom number optionally replaced is 1;R is the carbon optionally replaced
Direct-connected or branch naphthenic base that atomicity is 5, the straight chain aryl that the carbon atom number optionally replaced is 6, the carbon atom optionally replaced
Count the straight chain aralkyl for being 7, the straight chain hydroxyalkyl or hydroxyl that the carbon atom number optionally replaced is 1;X is 0.
The embodiment of the present invention two are as follows:
A kind of aluminum electrolytic condenser of the present embodiment, the oxidation voltage of the anode of the aluminum electrolytic condenser are 50V,
Including dispersion, it further includes additive that the dispersion, which includes conducting polymer, dispersing agent and polymeric anion, the addition
Agent is ether.The pH value of the dispersion is 7, and the viscosity of the dispersion at 20 °C is 400cps.The conducting polymer
The average grain diameter of object is 30nm.The conducting polymer includes polythiofuran derivative, further includes Polypyrrole derivatives and polyaniline
Derivative.The polymeric anion is polystyrolsulfon acid anion, and the molecular weight of the polystyrolsulfon acid anion is
500000, the dispersing agent is organic solvent.The polythiofuran derivative includes the repetitive unit that there is the following general formula II to form,
The structural formula of the general formula II are as follows:
In the structural formula of the general formula II, A is the alkylidene that the carbon atom number optionally replaced is 5;R is the carbon optionally replaced
Branch naphthenic base that atomicity is 12, the branch aryl that the carbon atom number optionally replaced is 14, the carbon atom number optionally replaced are
18 branched aralkyl groups, the branched chain hydroxy alkyl or hydroxyl that the carbon atom number optionally replaced is 4;X is 8.
The embodiment of the present invention three are as follows:
A kind of aluminum electrolytic condenser of the present embodiment, the oxidation voltage of the anode of the aluminum electrolytic condenser are 60V,
Including dispersion, it further includes additive that the dispersion, which includes conducting polymer, dispersing agent and polymeric anion, the addition
Agent is amide group.The pH value of the dispersion is 4, and the viscosity of the dispersion at 20 °C is 200cps.It is described to lead
The average grain diameter of electric polymer is 20nm.The conducting polymer includes polythiofuran derivative, further includes polyaniline derivative.Institute
Stating polymeric anion is polystyrolsulfon acid anion, and the molecular weight of the polystyrolsulfon acid anion is 300000, described
Dispersing agent is water.The polythiofuran derivative includes the repetitive unit with the following general formula I and general formula II composition, the general formula I
Structural formula are as follows:
The structural formula of the general formula II are as follows:
In the structural formula of the general formula I and the structural formula of general formula II, A is the alkylidene that the carbon atom number optionally replaced is 2;
R be the carbon atom number optionally replaced be 8 straight chain naphthenic base, the carbon atom number that optionally replaces be 10 straight chain aryl, optionally take
The branched chain hydroxy alkyl or hydroxyl that straight chain aralkyl that the carbon atom number in generation is 10, the carbon atom number optionally replaced are 3;X is 4.
The embodiment of the present invention four are as follows:
100g polystyrolsulfon acid (molecular weight 25000) is added in 2000g deionized water, stirring 30 minutes, then
By the sodium persulfate aqueous solution of 50g 35%, 1% ferric sulfate aqueous solution 14.4g and 9.1g 3, the mixing of 4- dialkoxythiophene
It is even added in above-mentioned aqueous solution, stirring is for 24 hours.After reaction, 200g resin cation, 200g are added into reaction system
Resin anion (R.A.) stirs 2h, filters out resin to get poly- (3,4- dialkoxythiophene) polyanion dispersion is arrived.It is equal with high pressure
Matter machine, under 1000bar pressure, homogeneous 5 times.Then solid content 1.34% is tested.With particle size analyzer test partial size in 10-
30nm.The viscosity 150cps of dispersion.
Poly- (3,4- dialkoxythiophene) polyanion, the 5g ethylene glycol, 5g polyethylene glycol that the 100g above method is obtained
600,0.5g3- glycidoxypropyl trimethyoxysilane (Silquest A-187), 0.5gDynol604 (Air
Product it) is mixed in glass beaker with magnetic stirring apparatus, forms dispersion B.
Include respectively above-mentioned dispersion B by the core of 4 kinds of specifications, drying is then carried out at 120 DEG C and its performance is carried out
Test.Test result such as table 1.Table 1 is that the core of 4 kinds of specifications includes the performance test table of dispersion B.
Table 1
The embodiment of the present invention five are as follows:
By poly- (3,4- dialkoxythiophene) the polyanion dispersion of 100g embodiment 1,5g dimethyl sulfoxide, the poly- second of 5g
Glycol 400,0.5g 3- glycidoxypropyl trimethyoxysilane (SilquestA-187), 2g sorbierite, 0.5g
Dynol604 (Air product) is mixed in glass beaker with magnetic stirring apparatus, forms dispersion C.
Include respectively the dispersion C by the core of 4 kinds of specifications, drying is then carried out at 120 DEG C and its performance is carried out
Test.Test result such as table 2.Table 2 is that the core of 4 kinds of specifications includes the performance test table of dispersion C.
Table 2
The embodiment of the present invention six are as follows:
By poly- (3,4- dialkoxythiophene) the polyanion dispersion of 100g embodiment 1,5g dimethyl sulfoxide, the poly- second of 5g
Glycol 200,0.5g 3- glycidoxypropyl trimethyoxysilane (SilquestA-187), 2g xylitol, 0.5g
Dynol604 (Air product) is mixed in glass beaker with magnetic stirring apparatus, forms dispersion D.
Include respectively dispersion D by the core of 4 kinds of specifications, then carries out drying and testing its performance at 120 DEG C.
Test result such as table 3.Table 3 is that the core of 4 kinds of specifications includes the performance test table of dispersion D.
Table 3
By table 1-3 it is found that the capacitor of aluminum electrolytic condenser of the invention be 10-220 μ F, DF value 1.4-1.6%, etc.
Effect series resistance is 6-18m Ω, has the advantages that go out to be easy, that low, equivalent series resistance is lost is low and leak electricity low.
To be easy, be lost that low, equivalent series resistance is low in conclusion aluminum electrolytic condenser provided by the invention has
And the advantage that electric leakage is low.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (9)
1. a kind of aluminum electrolytic condenser, which is characterized in that the oxidation voltage of the anode of the aluminum electrolytic condenser is greater than 30V
And oxidation voltage is less than or equal to 60V, including dispersion, the dispersion include conducting polymer and dispersing agent, the conduction
The average grain diameter of polymer is 20-30nm;The pH value of the dispersion is 1.5-7, the dispersion at 20 °C viscous
Degree is not more than 500cps.
2. aluminum electrolytic condenser according to claim 1, which is characterized in that the conducting polymer includes that polythiophene spreads out
Biology, the polythiofuran derivative include the repetitive unit that there is the following general formula I and/or general formula II to form, the knot of the general formula I
Structure formula are as follows:
The structural formula of the general formula II are as follows:
In the structural formula of the general formula I and the structural formula of general formula II, A is the alkylidene that the carbon atom number optionally replaced is 1-5;R
The straight chain that linear chain or branched chain naphthenic base that carbon atom number optionally to replace is 5-12, the carbon atom number optionally replaced are 6-14
Or branch aryl, the carbon atom number that optionally replaces be 7-18 linear chain or branched chain aralkyl, the carbon atom number that optionally replaces be 1-4
Linear chain or branched chain hydroxyalkyl or hydroxyl;X is the integer of 0-8.
3. aluminum electrolytic condenser according to claim 1, which is characterized in that the conducting polymer further includes polypyrrole
At least one of derivative and polyaniline derivative.
4. aluminum electrolytic condenser according to claim 1, which is characterized in that the dispersion further include polymerization yin from
Son.
5. aluminum electrolytic condenser according to claim 4, which is characterized in that the polymeric anion is polymerization of carboxylic acid yin
Ion or sulfonic acids anion.
6. aluminum electrolytic condenser according to claim 4, which is characterized in that the polymeric anion is polystyrene sulphur
Acid anion, the molecular weight of the polystyrolsulfon acid anion are 2000-500000.
7. aluminum electrolytic condenser according to claim 1, which is characterized in that the dispersing agent be organic solvent and/or
Water.
8. aluminum electrolytic condenser according to claim 1, which is characterized in that the dispersion further includes crosslinking agent, table
At least one of face activating agent and additive, the additive are selected from ether, lactone, amide group, lactams group, sulfone, Asia
At least one of sulfone, sugar, sugar derivatives, sugar alcohol, furan derivatives, dihydric alcohol and polyalcohol.
9. a kind of preparation method of aluminum electrolytic condenser, which is characterized in that the electricity of the aluminium described in claim 1-8 any one
Apply the dispersion on the electrode of chemical capacitor, then partly or entirely remove the dispersing agent, or will be described point
Powder is solidified, it is described removal or cured number be once or twice more than.
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