CN102820138A - Method of preparing intrinsic high-conductive polymer electrolytic capacitor by in-situ chemical oxidative polymerization - Google Patents
Method of preparing intrinsic high-conductive polymer electrolytic capacitor by in-situ chemical oxidative polymerization Download PDFInfo
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Abstract
The invention discloses a method of preparing an intrinsic high-conductive polymer electrolytic capacitor by in-situ chemical oxidative polymerization, which is realized in the way that the alkalinity or acidity of monomer solution through a modifier or in a modified solution atmosphere on the premise of in-situ chemical oxidative polymerization. Moreover, after modified solution is added, the speed of a polymerization reaction is accelerated, the electric conductivity and uniformity of a conductive polymer are improved, and therefore, the electrical property and production efficiency of the capacitor are greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of solid electrolytic capacitor, particularly the manufacture method of high conductivity polymer solid electrolyte capacitators.
Technical background
Along with the acceleration of electronic equipment digitlization and microminiaturized process, to the increasing demand crescendo of the low ESR of high band electronic component, the capacitor that particularly in these systems, uses requires its equivalent series resistance and inductance little, and high frequency performance is stable.The electrostrictive polymer electrolysis condenser receives much attention because of lower ESR.In order to obtain the electrostrictive polymer electrolysis condenser of ultralow ESR; Done a lot of work in the research and development of capacitor with in making; Comprise and use various monomers, adhesive, oxidant and dopant, its objective is feasible conducting polymer stability and the good conductivity that forms of the acting in conjunction that utilizes various materials.The dielectric substrate of electrostrictive polymer electrolysis condenser is one deck conducting polymer thin film of making through the method for in-situ chemical or electrochemical polymerization on the oxide film dielectric surface.Usually go on foot or two-stage polymerization method polymerization conducting polymer with one on the deielectric-coating surface.The two-step method that particularly generally adopts in the production process; Monomer solution is easy to by cross pollution in the dipping process, and a large amount of acid is deposited in dipping process in the monomer solution, makes monomer solution constantly degenerated by acidifying; Because continuous acid deposition; The pH value of solution can drop to continuously 3 or below, the conductivity of the conducting polymer of formation is more and more littler, thereby can not satisfy the requirement of ultralow ESR.According to United States Patent (USP) U.S. 7,754,276 B2 report, the pH value of used monomer solution surpasses 4, just can obtain the polymer of high conductivity.And the formation that reduces to show Bronsted acid of pH value, it has quickened the generation of byproduct of reaction, causes having formed in the polymerization reaction link of a lot of oligomer and non-conjugated ring.Non-conjugated ring has damaged the path of conduction electron, has therefore reduced the conductivity of main polymer chain.As 3; The appearance of acid can cause an acid catalyzed side reaction in 4-ethene dioxythiophene (EDOT) monomer solution; Form unconjugated dihydro-thiophene molecule, and the conductance of dihydro-thiophene molecule is very low, thereby receives the resistance of the influence increase conducting polymer of acid catalyzed reaction accessory substance dihydro-thiophene.Patent of the present invention proposes a kind of method of polymerization in alkaline atmosphere; Be through regulating the Acidity of Aikalinity of polymeric solution; Thereby in polymerization reactant, form pi-conjugated polymer long-chain; Improve the conductivity and the reaction speed of conducting polymer, thereby significantly reduce the ESR and the leakage current of conducting polymer capacitor.This conductive polymer applications can improve the electrical property of capacitor in solid electrolytic capacitor, obtains long stability and reliability.
Summary of the invention
The object of the invention is intended to quicken the speed of polymerization reaction, improves the conductivity of electric conductive polymer, makes that static capacity is big, leakage current is little, ESR and inductance is low, good stability, conducting polymer electrolytic capacitor that reliability is high.
The polymer of high conductivity; Particularly when conductivity is higher than 1000S/cm; Application to low ESR conducting polymer capacitor is extremely important, in order to obtain the electrostrictive polymer electrolysis condenser of ultralow ESR, in the research and development and making of capacitor; Attempted various oxidants and dopant, the acting in conjunction of various materials makes conducting polymer more stable.Recent findings, the pH value of used monomer solution surpasses 4, just can obtain the polymer of high conductivity, and the performance of the resistance of conductive polymer solution and the conducting polymer thin film of formation can obtain very big improvement.Highly purified monomer in use causes the acid deposition in the monomer solution owing to repeatedly flooding anode block, makes the pH value of solution reduce gradually.And the appearance of acid can cause an acid catalyzed side reaction in the monomer solution, causes forming the very low byproduct of reaction of conductance.
In order to make the polymer of high conductivity, acid catalyzed reaction must be forbidden, perhaps is suppressed to minimum to its negative effect at least; If do not suppress; Be lower than 3 because continuous acid deposition, the pH value of solution drop to continuously, be difficult to produce the electrolyte of the electrostrictive polymer electrolysis condenser that meets the demands.Because of the pH value is the indicating device of solution acidic, as long as the pH value of control monomer solution just can obtain the extraordinary thin polymer film of conductivity more than 4.But the pH value of monomer solution is also unsuitable excessive, and general the requirement is no more than 12, preferably is no more than 8.Therefore, the pH value of monomer solution should be controlled at 4-8, is more preferably at 4.5-6.5 preferred 5 ± 0.5.
Therefore, the acid that is deposited in the monomer with the alkali neutralization in the monomer solution can be controlled the generation of acid catalysis side reaction effectively, thereby keeps the high conductivity of conducting polymer.Normally used basic matterial comprises inorganic base and organic base, inorganic base such as metal oxide, metal hydroxides, alkaline rare earth metal oxide and hydroxide etc., and the cation that contains in the inorganic base that generally uses is Mg
2+, Ca
2+, Sr
2+, Ba
2+, Al
3+But do not comprise the transition metal cation, therefore, it can not have influence on conducting polymer.Basic organic base is mainly organic amine; Like dimethylamine, diethylamine, 1,3 propyl diamine, 1,2 propyl diamine; The alkanolamine and the acid amides that also have other; Like diethanol amine, methyl nitrosourea and N, dinethylformamide etc. are selected for use water-soluble and reasonable dimethylamine of volatility and diethylamine usually.The concentration of aqueous slkali is 0.2mol/L, preferred 0.8mol/L, and maximum is no more than 1.5mol/L.The polymerization reaction improver can be the liquid aqueous solution that gets, and also can be the steam of volatilization under the aqueous slkali normal temperature.Improver can be coated in the surface of anode block in advance, is covered behind the monomer/oxidant that perhaps has been covered again, perhaps join in monomer/oxidant, or before polymerization reaction/handle in the steam ambient of alkaline solution the back.The mass percent concentration of the reaction improver aqueous solution is 6%; The pH value of solution is 7-10, preferred 7-8, therefore; Said neutralization method telo merization thing above using, a large amount of bronsted lowry acids and bases bronsted lowries add allocates the monomer solution that just can meet the requirements of the pH value.
The monomer that forms conducting polymer among the present invention comprises thiophene, pyrroles and aniline and derivative thereof.The derivative of thiophene comprises 3,4-ethene dioxythiophene (EDOT), 3-alkylthrophene, 3-alkoxy thiophene, 3-alkyl 4-alkoxy thiophene, 3,4-dialkyl group thiophene, 3,4-dialkoxythiophene.Pyrroles's derivative comprises 3,4-alkyl pyrroles, 3,4-alkoxyl pyrroles.The derivative of aniline comprises 2-alkyl benzene amine, 2-alkoxyl aniline.Monomer in the polymerization reaction is liquid, but in order to make polymerization reaction smooth more, monomer need be used a kind of organic solvent diluting, and these organic solvents comprise methyl alcohol, ethanol, isopropyl alcohol, n-butanol, acetone and acetonitrile etc.
Be used as oxidant dopant with ferric ion salt, like iron chloride, ferric perchlorate, benzene sulfonic acid iron, p-methyl benzenesulfonic acid iron, naphthalene sulfonic acids iron and dibutyl naphthalene sulfonic acid iron etc.The p-methyl benzenesulfonic acid iron that preferred oxidation susceptibility is very excellent.The mass percent concentration of oxidant dopant solution is at least greater than 15%; Be more preferably greater than 20%,, just do not reach the oxidant dopant expected effect if the concentration of oxidant is too low; On the other hand; Concentration surpass 25% can accelerate polymerization reaction process, concentration surpasses 30% even 40% can satisfy the make efficiency of capacitor and the performance of solid electrolytic capacitor, the topmost application of conducting polymer that Here it is.Concentration surpasses 55% can produce better result, like low ESR and high power capacity.Yet the concentration of oxidant dopant surpasses 80%, and these performances can diminish on the contrary.The concentration of oxidant dopant solution should be high as much as possible according to the scope of above-mentioned adjusting.Use the reaction improver among the present invention to make conducting polymer, will improve the performance of make efficiency and solid electrolyte.
The forming process of conducting polymer comprises A among the present invention: the oxidant dipping process, and anode block immerses oxidizing agent solution, oxidant water or organic solvent diluting, weight ratio concentration is 15-55%, preferred 20-40%, dip time is 1s-5min; Process B: monomer dipping process, monomer are used a kind of organic solvent diluting, and weight ratio concentration is 5-100%, preferred 10-40%, and anode block immerses monomer solution 1s-5min; Process C is the processing procedure of reaction accelerator; With the anode block dipping alkaline solution that has flooded oxidant and monomer or in the alkaline steam environment, handle, be deposited on the acid in the monomer solution with the neutralization part, treatment temperature is a room temperature; Processing time is 1s-60min, is preferably 5min-30min; Process D polymerization process: the surface is covered with the anode block of monomer, oxidant and reaction accelerator at temperature 0-120 ℃, preferably polymerization reaction 1min-3h, preferably 10min-2h in 30-70 ℃ the environment.Process A, B, C, D respectively carry out once respectively, form conducting polymer, and in order to form fine and close conducting polymer rete, process A-D need repeat several times.
With 3,4-ethene dioxythiophene EDOT example is made the conducting polymer electrolyte of tantalum electrolytic capacitor, and detailed manufacturing process is:
Preparation by existing technology completion anode block surface dielectric oxide-film forms high conductive polymer cathode dielectric substrate through following operation on the anode block that generates dielectric oxide film:
1: it is 6% silane coupler that the anode block that the surface is formed dielectric oxide film immerses weight percent concentration, dip time 5min, and again at 50-100 ℃, relative humidity is dry 30min in the air ambient of 30%-70%;
2: the conductive polymer cathode film preparation comprises the processing of reaction accelerator and synthesizing of polymer
A: the oxidant dipping process, anode block immerses oxidizing agent solution, and dip time is 1s-5min; Oxidant water or organic solvent diluting, weight ratio concentration are 15-55%, preferred 20-40%;
B: monomer dipping process, monomer are used a kind of organic solvent diluting, and weight ratio concentration is 5-100%, preferred 10-40%, and the surface of anode block is the salting liquid of deposition reaction accelerator, and anode block immerses monomer solution 1s-5min;
C: be the processing procedure of reaction accelerator; The anode block that has flooded oxidant and monomer is placed in alkaline solution or the alkaline steam environment handles, be deposited on the acid in the monomer solution with neutralization, treatment temperature is a room temperature; Processing time is 1s-60min, is preferably 5min-30min;
D: polymerization process: the surface is covered with the anode block of monomer, oxidant and reaction accelerator at temperature 0-120 ℃, preferably polymerization reaction 1min-3h in 30-70 ℃ the environment, preferably 10min-2h;
E: in 70 ℃ deionized water, boil and wash 1h, dry 15min in 100 ℃ air ambient;
F: in p-methyl benzenesulfonic acid solution/phosphoric acid solution of 0.03%-0.05%, the dielectric oxide film layer is formed again, take out air drying 1h then at 150 ℃;
G: repeat above-mentioned A-F step 8-15 time.
3: accomplish to be covered with the electrolytical tantalum wicking surface of conducting polymer coated graphite layer and silver slurry layer successively by existing technology, and accomplish processes such as spot welding, bonding, group frame and mold pressing encapsulation, form final products after the shaping, and test its electrical property.
In sum; A kind of in-situ oxidizing-polymerizing of the present invention prepares the high conducting polymer electrolytic capacitor of intrinsic method; Comprise by operation before the existing technology and accomplishing with valve metal or valve metal oxides anode block as capacitor; Form dielectric oxide film on the anode block surface with electrochemical method and be covered with coated graphite layer and silver slurry layer on the high conductive polymer cathode dielectric substrate with back operation completion; And spot welding, bonding, group frame and press mold is encapsulated as finished product, it is characterized in that on the anode block that generates dielectric oxide film, forming high conductive polymer cathode dielectric substrate through following operation:
(1) it is the silane coupler aqueous solution of 5-6% that the anode block that the surface is formed dielectric oxide film immerses weight percent concentration, dip time 5min, and again at 50-100 ℃, relative humidity is dry 30min in the air ambient of 30%-70% relatively;
(2) form high conductive polymer cathode dielectric substrate: will handle by following method through the anode block that step (1) is handled:
A: the oxidant dipping process, anode block immerses aqueous oxidizing agent solution, and oxidant concentration 20-80%wt, dip time are 1s-5min, take out 23 ℃ of oven dry 60min, and the oxidizing agent solution of indication is a p-methyl benzenesulfonic acid molten iron solution;
B: monomer dipping process, monomer are used a kind of organic solvent diluting, and weight ratio concentration is 5-100%; Monomer solution pH 4-8, the anode block immersion monomer solution time of handling through A is 1s-5min, the monomer of indication is 3; 4-ethene dioxythiophene EDOT, organic solvent are ethanol;
C: the processing procedure of reaction accelerator; The anode block that has flooded oxidant and monomer is handled in alkaline solution or alkaline steam environment, be deposited on acid too much in the monomer solution with neutralization, alkali steam treatment temperature is a room temperature; Processing time is 1s-60min, and the indication alkaline solution is meant Ca (OH)
2Or Mg (OH)
2The aqueous solution, concentration 0.2-1.5mol/l, indication alkaline steam environment is meant dimethylamine or diethylamine steam ambient;
D: polymerization process: the surface is covered with anode block polymerization reaction 1min-3h in room temperature environment of monomer, oxidant and reaction accelerator;
E: in 60-70 ℃ deionized water, boil and wash 1h, dry 15min in 100 ℃ air ambient;
F: in p-methyl benzenesulfonic acid solution/phosphoric acid solution of 0.03%-0.05%, the dielectric oxide film layer is formed again, take out air drying 1h then at 150 ℃.
Above-mentioned steps (2) A oxidant also comprises benzene sulfonic acid iron, naphthalene sulfonic acids iron or butyl sulfonic acid iron.
Above-mentioned steps (2) B monomer also comprises thiophene, 3-alkylthrophene, 3-alkoxy thiophene, 3-alkyl 4-alkoxy thiophene or 3,4-dialkyl group thiophene, and organic solvent also comprises methyl alcohol, isopropyl alcohol.
The alkaline solution of above-mentioned steps (2) C indication also comprises Sr
2+, Ba
2+, Al
3+The aqueous solution.
Optimal conditions is: step (2) A aqueous oxidizing agent solution concentration 20-55%wt; Step (2) B monomer solution weight ratio concentration is 10-40%wt, monomer solution pH=4.5-6.5; Step (2) C alkali steam treatment temperature is a normal temperature, and the processing time is 5-30min; Alkaline solution C
a(OH)
2Or Mg (OH)
2Concentration of aqueous solution 0.8mol/l; The surface is covered with anode block polymerization 10min-2h in room temperature environment of monomer, oxidant and reaction accelerator;
In the step of the present invention (2), can be before oxide impregnation agent and monomer during step (2) C alkali steam treatment, promptly before step (2) A and (2) B, can also be afterwards in step (2) A and (2).
In the step of the present invention (2), process A, B, C and D carry out once respectively, and in order to form fine and close conducting polymer rete, A to D needs repetition 8-15 time.
The present invention is deposited on the acid in the monomer with the alkali neutralization, can control the generation of catalyze side reactions effectively, thereby keeps the high conductivity of conducting polymer.
Patent of the present invention proposes a kind of method of polymerization in alkaline atmosphere; Be through regulating the Acidity of Aikalinity of polymeric solution; Thereby in polymerization reactant, form pi-conjugated polymer long-chain; Improve the conductivity and the reaction speed of conducting polymer, thereby significantly reduce the ESR and the leakage current of conducting polymer capacitor.This conductive polymer applications can improve the electrical property of capacitor in solid electrolytic capacitor, obtains long stability and reliability.
The present invention does further detailed description with following by reference example, and these examples should not be construed as and limit this invention by any way.
The practical implementation example
Add a certain amount of adhesive in the Ta powder used in capacitor, moulded section is of a size of the tantalum piece of 3.1 * 0.9 * 4.6 (mm), and high-temperature vacuum sintering specific volume is 36,600 CV/g.Tantalum base behind these sintering is used in following examples.
Embodiment 1
It is 0.03% 20 ℃ phosphoric acid solution that tantalum base behind the sintering is placed concentration, adds the direct voltage of 55V, forms unbodied Ta through electrochemical reaction on tantalum base surface
2O
5Dielectric oxide film.The tantalum base that generates dielectric layer is immersed in the aqueous solution that weight concentration is 5% silane coupler, and dip time is 5min, again at 50-100 ℃
,Relative humidity is dry 30min in the air ambient of 30%-70%.The tantalum base that is covered with adhesive linkage is immersed in the sulfonate solution that weight percent concentration is 25% ferric ion, and dip time is 5 minutes, puts into temperature then and be 23 ℃ dry 60 minutes of baking oven.Flood weight percent concentration again and be the butyl acetate or derivatives thereof solution of 5% monomer, dip time is 5 minutes.The anode block that has flooded oxidant and monomer is put into the steam ambient of diethylamine aqueous solution and handled, treatment temperature is a room temperature, and the processing time is 60min.Put into temperature again and be 23 ℃ baking oven polymerization 90 minutes.In 60 ℃ deionized water, cleaned 60 minutes, after the polymerization, the surface of deielectric-coating has certain damage or destruction, mends in 0.03% p-methyl benzenesulfonic acid solution that to form to repair deielectric-coating, to put into temperature be 70 ℃ dry 15 minutes of baking oven.Whole process circulation 8-15 time.The product of drying is immersed graphite and silver slurry respectively.Carry out spot welding, bonding and mold pressing encapsulation then.At last the electrical quantity of capacitor is measured.Test result is seen table 1.
Comparative examples one
Product behind one group of sintering is carried out moulding according to embodiment one identical process conditions and energizes the aqueous solution formation adhesive layer of dipping silane coupler.The tantalum base that is covered with adhesive linkage is immersed in the sulfonate solution that weight percent concentration is 25% ferric ion, and dip time is 5 minutes, puts into temperature then and be 23 ℃ dry 60 minutes of baking oven.Flood monomer solution again, dip time is 5 minutes.Aqua calcis with 5% is handled and is filtered.Again with cleaning in 70 ℃ the deionized water 60 minutes, put into temperature after forming again and be 100 ℃ dry 15 minutes of baking oven.Product impregnated graphite and silver slurry, and at mold pressing encapsulation back test ESR and leakage current, concrete data are seen table 1.
Comparative examples two
Product behind one group of sintering is carried out moulding according to embodiment one identical process conditions and energizes the aqueous solution formation adhesive layer of dipping silane coupler.The tantalum base that is covered with adhesive linkage is immersed in the sulfonate solution that weight percent concentration is 25% ferric ion, and dip time is 5 minutes, puts into temperature then and be 23 ℃ dry 60 minutes of baking oven.Flood monomer solution again, dip time is 5 minutes.The dimethylamine with 5% or the solution-treated of diethylamine are also filtered.Again with cleaning in 70 ℃ the deionized water 60 minutes, put into temperature after forming again and be 100 ℃ dry 15 minutes of baking oven.Product impregnated graphite and silver slurry, and at mold pressing encapsulation back test ESR and leakage current.Concrete data are seen table 1.
Comparative examples three
The tantalum base that generates dielectric layer is immersed in the sulfonate solution that weight concentration is 25% ferric ion, and the impregnation time is 5 minutes, puts into temperature then and be 23 ℃ dry 30 minutes of baking oven.Impregnation weight concentration again is the butyl acetate or derivatives thereof solution of 5% monomer, and the impregnation time is 5 minutes, puts into temperature and be 23 ℃ dry 30 minutes of baking oven.Again with cleaning in 70 ℃ the deionized water 60 minutes, put into temperature after forming again and be 100 ℃ dry 15 minutes of baking oven.After the polymerization, the surface of deielectric-coating has certain damage or destruction, in 0.1% p-methyl benzenesulfonic acid solution, mends to form to repair deielectric-coating.Concrete data are seen table 1.
Table 1
| Sample | Processing mode | Capacity (μ F) | ESR(mΩ) | Leakage current (μ A) |
| Experiment 1 | Diethylamine steam | 44.5~47 | 15.5~18 | 0.8~1.9 |
| Contrast 1 | Ca(OH) 2Solution | 43~46.5 | 16~22 | 1.1~2.1 |
| Contrast 2 | Diethylamine/dimethylamine solution | 43.5~46.5 | 16~21 | 1.1~2.2 |
| Contrast 3 | Do not have | 42~45 | 18~30 | 1.4~2.8 |
The dielectric substrate of electrolytic capacitor to capacitor volume draw, power loss and equivalent series resistance etc. have significant effects, and leakage current, property at high and low temperature, temperature frequency characteristic, soldering resistance, useful life and the reliability etc. of electrolytic capacitor are also had very big influence.Patent of the present invention provides a kind of solid tantalum electrolytic capacitor and preparation method thereof, particularly the improved preparation method of solid conduction property polymer dielectric.This method neutralizes to the too much acid that deposits in the monomer solution according to the principle of acid-base neutralization, and having suppressed the acid catalysis side reaction must take place, and improves the conductance of conducting polymer greatly.Utilize the steam ambient of alkaline solution to handle to compare the direct treatment effect of alkaline solution better, and operation is simpler relatively.Can know from embodiment comparison as a result, utilize the electrical property of the electrostrictive polymer electrolysis condenser that the present invention makes to have greatly improved.
Claims (7)
1. an in-situ oxidizing-polymerizing prepares the high conducting polymer electrolytic capacitor of intrinsic method; Comprise by operation before the existing technology and accomplishing with valve metal or valve metal oxides anode block as capacitor; Form dielectric oxide film on the anode block surface with electrochemical method and be covered with coated graphite layer and silver slurry layer on the high conductive polymer cathode dielectric substrate with back operation completion; And spot welding, bonding, group frame and press mold is encapsulated as finished product, it is characterized in that on the anode block that generates dielectric oxide film, forming high conductive polymer cathode dielectric substrate through following operation:
(1) it is the silane coupler aqueous solution of 5-6% that the anode block that the surface is formed dielectric oxide film immerses weight percent concentration, dip time 5min, and again at 50-100 ℃, relative humidity is dry 30min in the air ambient of 30%-70%;
(2) form high conductive polymer cathode dielectric substrate: will handle by following method through the anode block that step (1) is handled:
A: the oxidant dipping process, anode block immerses aqueous oxidizing agent solution, and oxidant concentration 20-80%wt, dip time are 1s-5min, take out 23 ℃ of oven dry 60min, and the oxidizing agent solution of indication is a p-methyl benzenesulfonic acid molten iron solution;
B: monomer dipping process, monomer are used a kind of organic solvent diluting, and weight ratio concentration is 5-100%; Monomer solution pH 4-8, the anode block immersion monomer solution time of handling through A is 1s-5min, the monomer of indication is 3; 4-ethene dioxythiophene EDOT, organic solvent are ethanol;
C: the processing procedure of reaction accelerator; The anode block that has flooded oxidant and monomer is handled in alkaline solution or alkaline steam environment, be deposited on acid too much in the monomer solution with neutralization, alkali steam treatment temperature is a room temperature; Processing time is 1s-60min, and the indication alkaline solution is meant Ca (OH)
2Or Mg (OH)
2The aqueous solution, concentration 0.2-1.5mol/l, indication alkaline steam environment is meant dimethylamine or diethylamine steam ambient;
D: polymerization process: the surface is covered with anode block polymerization reaction 1min-3h in room temperature environment of monomer, oxidant and reaction accelerator;
E: in 60-70 ℃ deionized water, boil and wash 1h, dry 15min in 100 ℃ air ambient;
F: in p-methyl benzenesulfonic acid solution/phosphoric acid solution of 0.03%-0.05%, the dielectric oxide film layer is formed again, take out air drying 1h then at 150 ℃.
2. a kind of in-situ oxidizing-polymerizing according to claim 1 prepares the high conducting polymer electrolytic capacitor of intrinsic method, it is characterized in that step (2) A oxidant also comprises benzene sulfonic acid iron, naphthalene sulfonic acids iron or butyl sulfonic acid iron.
3. a kind of in-situ oxidizing-polymerizing according to claim 1 prepares the high conducting polymer electrolytic capacitor of intrinsic method; It is characterized in that step (2) B monomer also comprises thiophene, 3-alkylthrophene, 3-alkoxy thiophene, 3-alkyl 4-alkoxy thiophene or 3; 4-dialkyl group thiophene, organic solvent also comprises methyl alcohol, ethanol, isopropyl alcohol, n-butanol, acetone or acetonitrile etc.
4. a kind of in-situ oxidizing-polymerizing according to claim 1 prepares the high conducting polymer electrolytic capacitor of intrinsic method, it is characterized in that the alkaline solution of step (2) C indication also comprises Sr
2+, Ba
2+, Al
3+The aqueous solution.
5. a kind of in-situ oxidizing-polymerizing according to claim 1 prepares the high conducting polymer electrolytic capacitor of intrinsic method, it is characterized in that step (2) A aqueous oxidizing agent solution concentration 20-55%wt; Step (2) B monomer solution weight ratio concentration is 10-40%wt, monomer solution pH=4.5-6.5; Step (2) C alkali steam treatment temperature is a normal temperature, and the processing time is 5-30min; Alkaline solution Ca (OH)
2Or Mg (OH)
2Concentration of aqueous solution 0.8mol/l, step (2) D polymerization process 10min-2h.
6. a kind of in-situ oxidizing-polymerizing according to claim 1 prepares the high conducting polymer electrolytic capacitor of intrinsic method; Can be before oxide impregnation agent and monomer when it is characterized in that step (2) C alkali steam treatment; Promptly before step (2) A and (2) B, can also be afterwards in step (2) A and (2).
7. a kind of in-situ oxidizing-polymerizing according to claim 1 prepares the high conducting polymer electrolytic capacitor of intrinsic method; It is characterized in that in the step (2); Process A, B, C and D carry out once respectively, and in order to form fine and close conducting polymer rete, A to D needs repetition 8-15 time.
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| CN103489657A (en) * | 2013-10-17 | 2014-01-01 | 中国振华（集团）新云电子元器件有限责任公司 | Preparation method of high-conductivity polymer electrolytic capacitor |
| CN103753926A (en) * | 2014-01-16 | 2014-04-30 | 中科院广州化学有限公司 | High-conductivity polythiophene conductive coating layer and preparation method and application thereof |
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| CN110240721A (en) * | 2019-06-20 | 2019-09-17 | 江西科技师范大学 | A kind of preparation method of pi-conjugated monomer organic polymer thin film |
| US10763046B2 (en) | 2016-09-15 | 2020-09-01 | Avx Corporation | Solid electrolytic capacitor with improved leakage current |
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