CN102768903A - Method for manufacturing high-voltageconducting polymer electrolytic capacitor - Google Patents
Method for manufacturing high-voltageconducting polymer electrolytic capacitor Download PDFInfo
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- CN102768903A CN102768903A CN2012102811628A CN201210281162A CN102768903A CN 102768903 A CN102768903 A CN 102768903A CN 2012102811628 A CN2012102811628 A CN 2012102811628A CN 201210281162 A CN201210281162 A CN 201210281162A CN 102768903 A CN102768903 A CN 102768903A
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- conducting polymer
- dispersion liquid
- dispersant
- viscosity
- polymer
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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
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a method for manufacturing a high-voltageconducting polymer electrolytic capacitor, belonging to the technical field of manufacturing electronic components. The method comprises the following steps: manufacturing a medium oxidation film on the surface of a value metal anode block by former processes and coating a graphite layer and a silver paste layer on a dielectric layer of a conducting polymer by following processes in the prior art. The method is characterized in that an anode block for generating the medium oxidation film on an anode surface is soaked in conducting polymer dispersion solutions with different viscosities to form a conducting polymer electrolytic film with a certain thickness, namely, a conducting polymer catholyte layer. The conducting polymer catholyte layer is formed by soaking the anode block in the dispersion solutions with three viscosities, so that particles of polymers can be filled into micropores of the anode block deeply; therefore, the electrostatic capacity of the capacitor is increased and the equivalent series resistance (ESR) and leakage currents is reduced largely accordingly.
Description
Technical field
The present invention relates to a kind of preparation method of solid electrolytic capacitor, particularly be suitable for the manufacture method of the solid conduction property polymer dielectric capacitor of high voltage-rated.
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.The electrostrictive polymer electrolysis condenser is to make one deck conducting polymer dielectric substrate on the oxide film dielectric surface through the method for in-situ chemical polymerization or electrochemical polymerization.And there is very big defective in the electrolytical method of this making, and at first, the byproduct of the residue of reaction or reaction is difficult to clean up, and causes the voltage endurance capability of capacitor to descend; Secondly, utilize organic electrolysis capacitor withstand voltage usually all below 25V of chemical polymerization or electrochemical polymerization; In addition; Conducting polymer through chemical polymerization or electrochemical polymerization is extremely thin; Must be and will satisfy the electrolytical requirement of electrolytic capacitor cathode through the repetition of repeatedly polymerization～cleaning process; Not only greatly reduce production efficiency, and in high temperature polymerization process, be easy to damage dielectric oxide film.
The scientific and technical personnel of our company; For overcoming the said method defective; Aspect the method making conducting polymer dielectric substrate of in-situ chemical polymerization, done a large amount of work on the oxide film dielectric surface at the polymer dielectric capacitor; Reducing polymer dielectric capacitor equivalent resistance ESR and leakage current, aspect such as increase work efficiency has obtained certain achievement, and has declared multinomial national inventing patent.According to another background paper United States Patent (USP) U.S. Pat. Nos.7; 563,290, the A2 report shifts to an earlier date the slurry (abbreviation dispersion liquid) that polymerization forms conducting polymer with monomer and oxidant; Can shorten cycle of production greatly through the dipping dispersion liquid, the voltage endurance capability of capacitor also improves a lot simultaneously.But the capacitor volume extraction rate is low in this method, and ESR is also bigger.
Summary of the invention
The object of the invention is intended to overcome the problem that exists in the background paper method; Improve the lining rate of electric conductive polymer at porousness anode bodies internal void; And can not cause the damage of dielectric oxide film; The making static capacity is big, and ESR and leakage current are little, is adapted at the conducting polymer electrolytic capacitor that uses in high frequency and the hyperbaric environment.
Generally speaking, the method for making electrolytic capacitor cathode polymer dielectric has chemical polymerization and electrochemical polymerization method.Dielectric oxide film through chemical polymerization and electrochemical polymerization method form is frangible relatively and inhomogeneous, and in polymerization process, is easy to cause the damage of deielectric-coating.Mainly contain two factors and cause the inefficacy of dielectric oxide film, superfluous Fe after the first polymerization reaction
+ 3Byproduct Fe with reaction
+ 2Generally believe that these cations that exist at the interface of medium and polymer can cause the increase of medium leakage current, thereby around these ions, form very strong internal field, produce very high heat and make dielectric oxide film puncture.Another factor is based on the essential attribute of conducting polymer.Owing to form the monomer of conducting polymer oxidation-reduction reaction can take place, that is to say that they both can be oxidized, can be reduced again.And this redox performance is pressed with very big influence to the breakdown potential of polymer and medium interface.Wherein polymerization process itself in in-situ chemical polymerization or the electrochemical polymerization process rather than the last conducting polymer that forms play a major role to the reduction of puncture voltage.Through analyzing the variation of the puncture voltage in each stage in the polymerization process, can find that the reduction of dielectric oxide film puncture voltage mainly produces in the conducting polymer thin film forming process.It has been generally acknowledged that the charged active group of the oxidized formation of monomer, these active groups combine to form dimer in twos, also possibly form trimer simultaneously, and tetramer and other oligomer form cancellated polymer at last.And these oligomer have very high energy and very active.Therefore, these active groups not only can react each other in polymerization process, and can with tantalum pentoxide medium reaction, through in medium, injecting defective (electronics or hole), thereby significantly reduced the insulation property of medium.That is to say that the degeneration of medium insulation property is that the interaction by high energy active group and medium causes.Because these active groups are the intermediate products in the polymerization process, therefore the reduction of polymerization process medium performance is unavoidable in position.And the dispersion liquid that uses conducting polymer can effectively be avoided the generation of this type of problem.The dispersion liquid of conducting polymer is the solution of the good conductive polymer particles of polymerization in advance, comprises conductive polymer particles, polymerization anion and dispersant, and wherein dispersant is water or some other organic solvent.Immerse this dispersion liquid to anode block and in appropriate environments after the drying; Surface at the oxide isolation film forms the pi-conjugated conducting polymer thin film of one deck; And pi-conjugated conducting polymer has very high conductivity and thermal stability, is particularly suitable for the electrolyte as electrolytic capacitor.Pi-conjugated conducting polymer comprises polypyrrole, polythiophene, polyaniline and polyphenylene oxide etc. and derivative thereof.Of paramount importance is polythiophene; Normally used is wherein a kind of derivative, promptly gathers 3,4-ethene dioxythiophene (being abbreviated as PEDOT); Because of its oxide has very high conductivity; This polymer is widely used in solid electrolytic capacitor, and Organic Light Emitting Diode (OLED) is in many electronic devices such as organic solar batteries and organic field-effect tube.Therefore, utilize the leakage current of the electrolytic capacitor that the PEDOT dispersion liquid makes very little, can not produce any destruction, thereby have very high puncture voltage dielectric oxide film.
Dispersion liquid comprises conductive polymer particles, polyanion and dispersant, and conductive polymer particles is made up of a kind of thiophene, pyrroles or aniline at least, the polythiophene particle that the preferred conduction characteristic is good and temperature stability is high.Polythiophene can positively charged in construction unit, also can be electronegative, depend on the functional group on the branch chain, and positive charge is usually at the main chain of polythiophene, and negative electrical charge can be chosen by in sulfonate or the substituted free radical of the carboxylate functional group.As the electrolytical polythiophene of solid capacitor is neutral or cationic, and cationic only is meant and on the main chain of thiophene, has positive charge.Get the thiophene of cationic, cationic number greater than 1 less than number of repeating units.
Anion can be monomer or polymerization anion, and the latter also is referred to as polyanion.The polymerization anion is recommended to use single polyanion, because they are to the contribution that is formed with of polymeric membrane.And the size after their polymerizations is little, makes the thermally-stabilised better of conducting polymer thin film.Anionic polymer can be a carboxylic acid, and like polyacrylic acid, polymethylacrylic acid gathers horse Lay acid, gathers sulfonic acid, polystyrolsulfon acid and polyvinyl sulfonic acid, gather carboxylic acid and sulfonic acid also can with vinylcarboxylic acid and vinyl sulfonic acid copolymerization.Some single polyanions comprise the anion of p-methyl benzenesulfonic acid, pyrovinic acid, camphorsulfonic acid and the rare sulfonic acid of polyphenyl, and wherein polystyrolsulfon acid (PSS) anion is a kind of good especially single polyanion.In the dispersion liquid weight ratio of polyanion and conductive polymer particles be 0.5:1 to 50:1, relatively suitable is 1.0:1 is to 40:1, preferred 1.5:1 is to 20:1.
The dispersant of conducting polymer dispersion liquid does not have a lot of restrictions, comprises water and alcohols and derivative thereof, and the alcohols of selecting for use usually comprises methyl alcohol, ethanol, isopropyl alcohol, n-butanol etc.Other ketone such as acetone in addition, methyl ethyl ketone; The aliphatic carboxylic acid esters,, like ethyl acetate, butyl acetate; Aromatic compound is like toluene and xylenes etc.The mixture of general water or water and these organic solvents is preferably used deionized water and ethanol as dispersant, and wherein water is preferred dispersing agent.The pH value 1～13 of dispersant, to mordant medium, in order not destroy medium, pH value is chosen as 4～8.In addition, can add the pH value that dispersion liquid is regulated in acid such as an amount of, but these acid can not there be damage effect to the formation of film in the dispersion liquid, and non-volatile when high temperature, still can stay in the electrolyte.
Adding dopant in the dispersion liquid does not have special limitation, as long as can evenly mix with pi-conjugated conducting polymer and polyanion.Operable additive comprises alkali compounds, surfactant, conduction reinforcing agent, adhesive etc.
Traditional inorganic alkaline compound and organic basic compound can use.Inorganic alkaline compound comprises NaOH, potassium hydroxide, calcium hydroxide and ammoniacal liquor etc.Organic basic compound comprises fatty amine, aromatic amine, and nitrogen-containing compound and other amine, metal alkoxide and methyl-sulfoxide etc. are according to increasing conductivity to greatest extent, preferred fat amine, aromatic amine.Surfactant comprises anion surfactant such as carboxylate, sulfonate, sulfate and phosphate; Cationic surfactant comprises amine salt, amphoteric surfactant carboxylic acid betaine, carboxylic acid ammonia; The imidazoles betaine uses more nonionic surfactant, like polyoxyethylene alkyl ether; Polyoxyethylene glycerine fatty acid ester, ethylene propylene three alcohol fatty acid esters, polyoxyethylene fatty acid ammonia.The conduction reinforcing agent that adds in the dispersion liquid comprises oxolane, the compound of lactone functional group (like gamma-butyrolacton, gamma-valerolactone), and amino or lactams functional compounds are (like caprolactam; The N-methyl caprolactam, N, N-dimethylacetylamide; The N-methylacetamide, N, dinethylformamide (DMF); The N-NMF), N-methyl pyrrolidone (NMP), N-octylpyrrolidone; Pyrrolidones, sulfone and sulfoxide are like sulfolane (tetramethylene sulfone) and dimethyl sulfoxide (DMSO) (DMSO); Carbohydrate or carbohydrate derivative, sucrose, glucose, fructose and lactose; Sugar alcohol, like D-sorbite, mannitol, furan derivatives such as methyl 2-furoate, N-methyl nitrosourea wherein, N-methyl pyrrolidone, ethylene glycol, methyl-sulfoxide and sorbierite are the conductivity reinforcing agents of recommending.Can be dissolved in bonding agent such as polyvinyl acetate in the organic dispersing agent, Merlon, polyvinyl butyral resin, polyacrylate; Polymethacrylates, polystyrene, polyacrylonitrile, polyvinyl chloride; Polybutadiene, isoprene, organosilicon or phenylethylene ethylene/propenoic acid ester, vinyl acetate/acrylic acid ester; Pyrroles/acrylic acid ester, ethylene/acetic acid ethyl ester copolymer, ethylene/vinyl acetate copolymer; The adhesive of good water solubility is like polyvinyl alcohol etc.
Low viscosity solution is equivalent to intermediate adhesion layer.Through polymeric, conductive layer at dielectric oxide film surface-coated low concentration, promptly can play the effect of repairing the oxide film dielectric defective, can increase conducting polymer rete and dielectric oxide film bonding strength again.The viscosity of low viscosity conducting polymer is 5～50mPas, is more preferably at 8～40mPas, and optimum is 10～20mPas.Flood the dispersion liquid of low viscous conducting polymer, can improve the permeability of solution in the porousness anode block.Increase the infiltrative while of dispersion liquid, must make as much as possible that the formation film is even, therefore, the viscosity of low viscosity solution is at least 5mPas, otherwise the quality of the conducting polymer thin film of formation descends, and has also reduced the efficient of producing.The average diameter of conductive polymer particles is 1～50nm in the low viscosity dispersion liquid, considers impregnability and make efficiency simultaneously, optional 5～40nm, preferably 10～20nm.When reducing solution viscosity, the solids content in the dispersion liquid must reduce accordingly, could effectively improve the permeability of solution.Solid content is 0.5-5% in the dispersion liquid of low viscous conducting polymer, and that more moderate is 1.2-3.5%, preferred 1.5-2.5%.The weight ratio of anion and conductive polymer particles can be more preferably the scope to 30:1 at 1.0:1 in the scope of 0.5:1 to 50:1, and preferred 1.5:1 is to the scope of 20:1.Solid content concentration at least 0.5% can easily form conducting polymer thin film.But it is thick that this layer conducting polymer is unfit to do, as long as the surface of ability overwrite media oxide-film is flooded low viscous conductive polymer solution usually and got final product for 1 time, is no more than at most 2 times, is called the ground floor conducting polymer.
The pH value of low viscosity solution relatively suits in 3～13 scopes, to be preferably in 5～11 scopes, and the pH value minimum of the low viscous solution that provides is 3, can reduce container and electrolytical corrosion, and leakage current is better.The pH value can not surpass 13, otherwise electrolytical conductivity can be suppressed.The pH value of solution can be carried out suitable adjustment through adding alkali compounds, and traditional inorganic alkaline compound or organic basic compound can be used.
Reduce the viscosity of conducting polymer dispersion liquid and can use the solid content that contains low concentration; The polyanion of lower molecular weight; With low viscous solvent, perhaps strengthen the dispersiveness of pi-conjugated conducting polymer, wherein strengthen the dispersed method of conducting polymer and comprise the high pressure dispersion method; Ultrasonic dispersion and high-velocity fluid dispersion method etc.These methods can be used wherein any one separately, also can merge two kinds or more method.
Increase the solution of the thickness of conducting polymer dielectric substrate with a kind of viscosity higher, the major function of this solution is to realize the growth of polyelectrolyte floor, also wants fully to be penetrated into the hole of porousness anode block.This conducting polymer dispersion liquid can effectively combine with the ground floor conducting polymer, can grow fast on the surface of anode block again, thereby form the polymer cathode layer with certain thickness electrolytic capacitor.The viscosity of viscosity higher conducting polymer is 8～80mPas, is more preferably at 10～60mPas, and optimum is 12～35mPas.Simultaneously, the diameter liquid of conductive polymer particles increases thereupon in the viscosity higher dispersion liquid, and the average diameter of conductive polymer particles is 5～100nm usually, and that more moderate is 10～80nm, preferably at 15～50nm.This layer mainly is the thickness that increases the conducting polymer rete, and therefore, the solid content in the conducting polymer dispersion liquid is higher relatively; The weight percent concentration scope is 1.5-10%; Be more preferably 2.0-5%, the least concentration of the solid content that provides is 1.5%, and conducting polymer is easy in layer superpose; Can not surpass 10.0%, so that conductive polymer solution is easy to be penetrated in the porous body.The weight ratio of anion and conductive polymer particles can be more preferably the scope to 30:1 at 1.5:1 in the scope of 1:1 to 50:1, and preferred 2:1 is to the scope of 20:1.The conducting polymer of viscosity higher disperses fluid power effectively to be penetrated into the hole of porousness anode block; Can grow fast on the anode block surface again; And bonding fine through ground floor conductive polymer coating and dielectric oxide film layer, play a key effect thereby draw and reduce ESR for the static capacity of capacitor.This polymer film is the major part of dielectric substrate, and the dipping number of times is more relatively, floods usually more than 3～5 times, is called second layer conducting polymer.Flooding more number of times, to be penetrated into inside, anode space by dispersion liquid be useful, can increase the thickness of conducting polymer or improve the coverage rate of conducting polymer.
In the process that forms solid electrolyte layer, use some drying means, dry like hot-air; Infrared heating is dry; The processing of conducting polymer thin film form is carried out in perhaps vacuumize, and the conductive polymer solution that is about to be covered is cured as the conducting polymer thin film on the dielectric layer surface of capacitor.In this process, the solution that contains pi-conjugated conductive polymer particles, polyanion and dispersant is as conductive polymer solution, and dry back forms pi-conjugated conducting polymer thin film.
Adopt the surface-coated layer of a kind of full-bodied conducting polymer dispersion liquid, to improve the mechanical strength on surface as polymer dielectric.The viscosity of high viscosity conducting polymer dispersion liquid is 50～300mPas, is more preferably at 60～200mPas, and optimum is 70～150mPas.The viscosity of high viscosity solution is 50mPas at least, the film thickness that just can obtain expecting with minimum number of repetition.Viscosity can not surpass 300mPas, otherwise the uniformity of film just can not satisfy.Simultaneously, the diameter of conductive polymer particles also increases thereupon in the high viscosity dispersion liquid, and the average diameter of conductive polymer particles is 50～300nm usually, and that more moderate is 80～250nm, preferably at 100～220nm.This layer mainly is the mechanical strength that increases the conducting polymer rete, and therefore, the solid content in the conducting polymer dispersion liquid is lower, generally is 0.5-3%, and that more moderate is 0.8-2.5%, preferred 1-2%.The weight ratio of anion and conductive polymer particles can be more preferably the scope to 30:1 at 1.5:1 in the scope of 1:1 to 50:1, and preferred 2:1 is to the scope of 20:1.Full-bodied conducting polymer dispersion liquid is overlayed on second layer conducting polymer surface, and dip time is shorter relatively, repeats 1～2 time and gets final product.
The method that increases solution viscosity also comprises the concentration that increases solid content in the conducting polymer solution.Use the polyanion of HMW, add full-bodied solvent, add the dispersant that increases thickness, perhaps add the content of resin.Above these methods can use separately, also can two or more be used in combination.
The dispersant of high viscosity solution is the solvent of macromolecule, like polyethylene glycol (molecular weight 2000 or bigger) etc.In order to satisfy the formation of the ground floor conducting polymer on dielectric layer surface fully, and guarantee the formation of other conducting polymer on the conducting polymer, the viscosity difference of high viscosity solution and low-viscosity solution is 50mPas at least.And according to practice, the viscosity difference of high viscosity solution and low-viscosity solution can not surpass 300mPas at most.The solution of low-viscosity wants to be penetrated into the inside of porousness anode block, and full-bodied solution is used for increasing the thickness of conducting polymer rete, uses full-bodied solution can reduce the number of times of dipping, enhances productivity.
After using dispersion liquid, dispersant is preferably removed, to form pi-conjugated conducting polymer solid electrolyte layer.Yet, still can remain in the conducting polymer electrolyte by some dispersant.Can remove dispersant through the method for simple room temperature volatilization, yet, obtain higher processing speed, it also is very useful that elevated temperature is removed dispersant, as from 20～300 ℃ of room temperatures, better heat-treats at 40～250 ℃.Be used in combination hot reprocessing, dry such as hot-air, the dry or vacuumize of infra-red heat can accelerate to remove dispersant, and hot reprocessing can be carried out after the conducting polymer rete forms or after each product overlay film.Heat treatment period will be decided according to the characteristics of the dispersion liquid that uses from 5min to the several hrs, and Temperature Distribution under the different temperatures and dwell time all will be considered in heat treatment.From the anode block surface removal dispersant of oxidation, and after the drying, especially after several dippings and drying cycles, the coverage rate of the polymer film of formation is higher, and ESR is littler.The particle of remaining conducting polymer also can remove from the outer surface of electric conductor, for example, with ultrasonic, laser beam, solvent or mechanical separation.
With the valve metal tantalum is example, and the detailed preparation process of this method comprises:
The first step: accomplish the preparation of tantalum anode piece surface dielectric oxide-film by existing technology;
Second step: 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 ℃;
The 3rd step: the processing of ground floor conducting polymer rete:
A) said ground floor conducting polymer rete obtains through flooding low viscous polymer dispersion liquid;
B) outfit of low viscous polymer dispersion liquid;
1) said low viscous polymer dispersion liquid comprises conductive polymer particles, polymerization anion and dispersant, and surfactant and adhesive;
2) said conductive polymer particles is that pi-conjugated conducting polymer comprises polypyrrole, polythiophene, polyaniline, polyacetylene and polyphenylene oxide etc. and derivative thereof, the PEDOT of preferred conduction property and Heat stability is good; Solid content is 0.5～5%; More moderate is 1.2～3.5%, preferred 1.5～2.5%, and the weight ratio of anion and conductive polymer particles can be in the scope of 0.5:1 to 50:1; Be more preferably the scope to 30:1 at 1.0:1, preferred 1.5:1 is to the scope of 20:1.
3) viscosity of low viscosity conducting polymer is 5～50mPas, is more preferably at 8～40mPas, and optimum is 10～20mPas;
4) said polyanion is the anion that comprises p-methyl benzenesulfonic acid, pyrovinic acid, camphorsulfonic acid and polyphenyl alkene sulfonic acid, and wherein polystyrolsulfon acid (PSS) anion is a kind of good especially single polyanion;
5) said dispersant is water and alcohols and derivative thereof, and the alcohols of selecting for use usually comprises methyl alcohol, ethanol, and isopropyl alcohol, n-butanol etc., wherein water is preferred dispersing agent;
6) said surfactant is a nonionic surfactant, like polyoxyethylene alkyl ether, and polyoxyethylene glycerine fatty acid ester, ethylene propylene three alcohol fatty acid esters, polyoxyethylene fatty acid ammonia, content are 0.01～0.3%, more moderate is 0.03～0.15%;
7) said adhesive is a polyvinyl acetate, Merlon, and polyvinyl butyral resin, polyacrylate, polymethacrylates, polystyrene, polyacrylonitrile, polyvinyl chloride etc., content are 0.03～0.3%, more moderate is 0.05～0.2%;
C) dipping temperature is a room temperature, dip time 5min;
D) utilize the method for room temperature volatilization to remove dispersant, be 0.5～1 hour drying time;
E) remove dispersant in the hot environment drying, baking temperature is 40～300 ℃, and more moderate is 50～250 ℃, and be 5～30min drying time;
11) repeat said process c～e one to secondary;
The 4th step: the preparation of second layer conductive polymer membrane
A) the conducting polymer dispersion liquid of preparation viscosity higher;
1) polymer dispersion liquid of said viscosity higher comprises conductive polymer particles, polymerization anion and dispersant, and conduction reinforcing agent and adhesive;
2) viscosity of viscosity higher conducting polymer is 8～80mPas, is more preferably at 10～60mPas, and optimum is 12～35mPas;
3) said conductive polymer particles is that pi-conjugated conducting polymer comprises polypyrrole; Polythiophene, polyaniline, polyacetylene and polyphenylene oxide etc. and derivative thereof, the PEDOT of preferred conduction property and Heat stability is good, solid content are 1.5～10%; Be more preferably 2.0～5%; The weight ratio of anion and conductive polymer particles can be more preferably the scope to 30:1 at 1.5:1 in the scope of 1:1 to 50:1, and preferred 2:1 is to the scope of 20:1;
4) said polyanion is the anion that comprises p-methyl benzenesulfonic acid, pyrovinic acid, camphorsulfonic acid and polyphenyl alkene sulfonic acid, and wherein polystyrolsulfon acid (PSS) anion is a kind of good especially single polyanion;
5) said dispersant is water and alcohols and derivative thereof, and the alcohols of selecting for use usually comprises methyl alcohol, ethanol, and isopropyl alcohol, n-butanols etc. are preferably used deionized water and ethanol, and wherein water is preferred dispersing agent;
6) said conduction reinforcing agent is an oxolane, N, dinethylformamide (DMF); The N-NMF, N-NMF, N-methyl pyrrolidone (NMP); The N-octylpyrrolidone, pyrrolidones, sulfone and sulfoxide; Like sulfolane (tetramethylene sulfone) and dimethyl sulfoxide (DMSO) (DMSO) etc., content is 0.01～0.3%, and more moderate is 0.03～0.15%;
7) said adhesive is a polyvinyl acetate, Merlon, and polyvinyl butyral resin, polyacrylate, polymethacrylates, polystyrene, polyacrylonitrile, polyvinyl chloride etc., content are 0.03～0.3%, more moderate is 0.05～0.2%;
B) dipping temperature is a room temperature, dip time 1～3min;
C) utilize the method for room temperature volatilization to remove dispersant, be 0.5～1 hour drying time;
D) remove dispersant in the hot environment drying, baking temperature is 40～300 ℃, and more moderate is 50～250 ℃, and be 5～40min drying time;
E) repeat said process b～d three to five times;
The 5th step: the preparation of the 3rd layer of conducting polymer thin film
A) the full-bodied conducting polymer dispersion liquid of preparation;
1) said full-bodied polymer dispersion liquid comprises conductive polymer particles, polymerization anion, dispersant and adhesive;
2) viscosity of high viscosity conducting polymer dispersion liquid is 50～300mPas, is more preferably at 60～200mPas, and optimum is 70～150mPas;
3) said conductive polymer particles is that pi-conjugated conducting polymer comprises polypyrrole, polythiophene, polyaniline, polyacetylene and polyphenylene oxide etc. and derivative thereof, the PEDOT of preferred conduction property and Heat stability is good; Solid content is 0.5～3%; More moderate is 0.8～2.5%, preferred 1～2%, and the weight ratio of anion and conductive polymer particles can be in the scope of 1:1 to 50:1; Be more preferably the scope to 30:1 at 1.5:1, preferred 2:1 is to the scope of 20:1;
4) said polyanion is the anion that comprises p-methyl benzenesulfonic acid, pyrovinic acid, camphorsulfonic acid and polyphenyl alkene sulfonic acid, and wherein polystyrolsulfon acid (PSS) anion is a kind of good especially single polyanion;
5) said dispersant is water and alcohols and derivative thereof, and the alcohols of selecting for use usually comprises methyl alcohol, ethanol, and isopropyl alcohol, n-butanols etc. are preferably used deionized water and ethanol, and wherein water is preferred dispersing agent;
6) said adhesive is a polyvinyl acetate, Merlon, and polyvinyl butyral resin, polyacrylate, polymethacrylates, polystyrene, polyacrylonitrile, polyvinyl chloride etc., content are 0.03～0.3%, more moderate is 0.05～0.2%;
B) dipping temperature is a room temperature, dip time 0.5～2min;
C) utilize the method for room temperature volatilization to remove dispersant, be 0.5～2 hour drying time;
D) remove dispersant in the hot environment drying, baking temperature is 40～300 ℃, and more moderate is 50～250 ℃, and be 5～20min drying time;
E) said process b～d repeats 1～2 time;
The 6th step: 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 spot welding, bonding, group frame and mold pressing encapsulate, form final products after the shaping, and test its electrical property.
Top manufacturing process is not used chemical oxidising polymerisation, even the conducting polymer rete can not bear very high voltage through cleaning yet.Therefore, clean link and can omit, thereby simplified manufacture method, improved the production efficiency of capacitor.According to the capacitor that this method is made, because the particle of dispersant can enter into the depths of the pin hole of porousness anode block, thereby capacitor has very high static capacity and lower ESR.
In sum; The manufacture method of a kind of high pressure conducting polymer of the present invention electrolytic condenser; Comprise by the preparation of operation valve metal anode block surface dielectric oxide-film before the existing technology and finishing operation accomplish be covered with on the conductive polymer cathode dielectric layer coated graphite layer and silver slurry layer and spot welding, bonding, organize frame and pressing mold is encapsulated as finished product; The anode block that it is characterized in that anode surface is generated dielectric oxide film is through dipping different viscosities conducting polymer dispersion liquid; Flood low viscous conducting polymer dispersion liquid as one deck adhesive linkage; The conducting polymer dispersion liquid of dipping viscosity higher forms the catholyte layer of capacitor, floods the surface-coated layer that full-bodied conducting polymer dispersion liquid forms solid electrolyte again; In normal temperature and hot environment, remove the dispersant in the dispersion liquid respectively; Forming certain thickness conducting polymer is the conductive polymer cathode dielectric substrate; Said dispersion liquid is by conductive polymer particles, polymerization anion and dispersant, and surfactant, conduction reinforcing agent and binder combination form; Conductive polymer particles is that pi-conjugated conducting polymer comprises polypyrrole, polythiophene, polyaniline and polyphenylene oxide etc. and derivative thereof; Said polymerization anion is the anion of p-methyl benzenesulfonic acid, pyrovinic acid, camphorsulfonic acid and polyphenyl alkene sulfonic acid; Dispersant is water and alcohols and derivative thereof, and the alcohols of selecting for use usually comprises methyl alcohol, ethanol, isopropyl alcohol, n-butanol; Described surfactant is a nonionic surfactant, comprises polyoxyethylene alkyl ether, polyoxyethylene glycerine fatty acid ester; Said conduction reinforcing agent comprises oxolane, N, dinethylformamide (DMF); Said adhesive comprises polyvinyl acetate, polystyrene, polyvinyl chloride; Its proportioning is polymer beads 0.5～10wt%, polymerization anion percetage by weight 2%～66%, activating agent 0～0.3 wt%; Reinforcing agent is 0～0.3 wt%, and adhesive is 0.03～0.3 wt%, and all the other are dispersant.
The indication polymer beads is preferred 3,4-vinyl dioxy thiophene; The preferred polystyrolsulfon acid of polymer anion (PSS); The dispersant preferred water; Surfactant also comprises ethylene propylene three alcohol fatty acid esters, polyoxyethylene fatty acid ammonia; The conduction reinforcing agent also comprises the N-methyl caprolactam, N-methyl pyrrolidone (NMP), N-octylpyrrolidone, pyrrolidones, sulfone and sulfoxide, tetramethylene sulfone, dimethyl sulfoxide (DMSO); Bonding agent also comprises Merlon, polyvinyl butyral resin, polyacrylate, polymethacrylates, polyacrylonitrile.
Low viscosity conducting polymer dispersion liquid is by conductive polymer particles; Polymer anion, dispersant, activating agent, adhesive are formed, and proportioning is conductive polymer particles 0.5～5wt%, polymer anion percetage by weight 2%～66%; Activating agent 0.01～0.3wt%; Adhesive 0.03～0.3wt%, all the other are dispersant, the viscosity of low viscosity conducting polymer dispersion liquid is 5～50mPas.
Viscosity higher conducting polymer dispersion liquid is by conductive polymer particles; Polymer anion, dispersant, reinforcing agent and adhesive are formed, and proportioning is a conductive polymer particles 1.5～10%, polymer anion percetage by weight 2%～50%; Reinforcing agent 0.01～0.3wt%; Adhesive 0.03～0.3wt%, all the other are dispersant, the viscosity of the conducting polymer dispersion liquid of viscosity higher is 8～80mPas.
Above-mentioned high viscosity conducting polymer dispersion liquid is by conductive polymer particles; Polymer anion, dispersant and adhesive are formed; Proportioning is conductive polymer particles 0.5～3wt%, polymer anion percetage by weight 2%～50%, adhesive 0.03～0.3wt%; All the other are dispersant, and the viscosity of full-bodied conducting polymer dispersion liquid is 50～300mPas.
The proportioning of above-mentioned each component of low viscosity conducting polymer dispersion liquid is: conductive polymer particles 1.5～2.5wt%; Polymer anion percetage by weight 4.7%～40%, activating agent 0.01～0.3wt%, adhesive 0.03～0.15wt%; All the other are dispersant, and the viscosity of dispersion liquid is 10～20mPas.
The proportioning of above-mentioned each component of viscosity higher conducting polymer dispersion liquid is: conductive polymer particles 2.0～5wt%; Polymer anion percetage by weight 4.7%～33%, reinforcing agent 0.03～0.15wt%, adhesive 0.05～0.2wt%; All the other are dispersant, and the viscosity of dispersion liquid is 12～35mPas.
The proportioning of above-mentioned each component of high viscosity conducting polymer dispersion liquid is: conductive polymer particles 1～2wt%; Polymer anion percetage by weight 4.7%～33%; Adhesive 0.05～0.2wt%, all the other are dispersant, the viscosity of full-bodied conducting polymer dispersion liquid is 70～150mPas.
The anode block that above-mentioned anode surface generates dielectric oxide film all will be done dipping next time after flooding the conducting polymer dispersion liquid of different viscosities at every turn again after removing dispersion liquid; Dipping low viscosity conducting polymer dispersion liquid will repeat 1～2 time; Dipping viscosity higher conducting polymer dispersion liquid will repeat 3～5 times, and dipping high viscosity conducting polymer dispersion liquid will repeat 1～2 time.
The present invention removes the method for dispersant with room temperature volatilization and high temperature drying, and the volatilization time is 0.3-2h, 50～250 ℃ of high temperature drying temperature, and be 5-40min drying time.
Patent of the present invention adopts the dispersion liquid of three kinds of different viscosities to flood respectively; Promptly flood low viscous dispersion liquid earlier as electrolytical internal layer; Flood the dispersion liquid of viscosity higher again; And form in the electrolytical surperficial continued growth of internal layer and to have certain thickness conducting polymer electrolyte, the full-bodied dispersion liquid of final impregnating forms electrolytical superficial layer.This method can make polymer particulates be filled into the micropore depths in the anode block, thereby has increased the static capacity of capacitor, and ESR is also corresponding with leakage current significantly reduces.
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.
Embodiment 1
Below use product to be 16V47 μ F in the test.
It is 0.03% 60 phosphoric acid solution that tantalum piece behind the sintering is placed concentration, adds the direct voltage of 55V, forms unbodied Ta through electrochemical reaction on tantalum piece surface
2O
5Medium.It is in the 15mPas conducting polymer dispersion liquid that the tantalum piece that generates dielectric layer is immersed viscosity, and dip time is 5min, then dry 30min in 25～50 ℃ air ambient, dry 30min in 80～150 ℃ air ambient again.It is 12～35mPas conducting polymer dispersion liquid that the tantalum piece that is covered with the first conducting polymer rete is immersed viscosity; Dip time is 3min; Dry 30min in 25～50 ℃ air ambient then, dry 40min in 80～200 ℃ air ambient repeats this process 3～5 times again.It is 45～125mPas conducting polymer dispersion liquid that the tantalum piece that is covered with the second conducting polymer rete is immersed viscosity, and dip time is 1min, then dry 90min in 25～50 ℃ air ambient, dry 20min in 80～200 ℃ air ambient again.
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.
Embodiment two
The tantalum piece that generates dielectric layer is immersed dipping p-methyl benzenesulfonic acid solution 5min, flood 3 again, 4-vinyl dioxy thiophene (EDOT) monomer solution 5min is at 25～30 ℃
,Relative humidity is polymerization reaction take place 60min in 30%～70% the air ambient, washes residual monomers and byproduct of reaction again, forms one deck conducting polymer thin film (PEDOT) thereby reoxidize the deielectric-coating surface, and this process repeats 6 times.The anode block that will be covered with conducting polymer thin film again immerses the dispersion liquid of conducting polymer, forms certain thickness polyelectrolyte floor.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
The tantalum piece that generates dielectric layer is immersed dipping p-methyl benzenesulfonic acid solution 5min, flood 3 again, 4-vinyl dioxy thiophene (EDOT) monomer solution 5min is at 25～30 ℃
,Relative humidity is polymerization reaction take place 60min in 30%～70% the air ambient; Wash residual monomers and byproduct of reaction again; Thereby reoxidize the deielectric-coating surface and form one deck conducting polymer thin film (PEDOT), this process repeats 6 times, increases the concentration of monomer and oxidant.Repeat said process 6～10 times, form certain thickness polyelectrolyte floor.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.
Table 1
| Sample | Capacity (μ F) | ESR(mΩ) | Leakage current (μ A) | Loss (%) | Puncture voltage (V) |
| Experiment 1 | 45 | 26.5 | 1.2 | 1.8 | >;45 |
| Experiment 2 | 43 | 32 | 1.9 | 2.0 | 36 |
| Contrast 1 | 42 | 37 | 3.4 | 2.6 | 25 |
Claims (10)
1. the manufacture method of a high pressure conducting polymer electrolytic condenser; Comprise by the preparation of operation valve metal anode block surface dielectric oxide-film before the existing technology and finishing operation accomplish be covered with on the conductive polymer cathode dielectric layer coated graphite layer and silver slurry layer and spot welding, bonding, organize frame and pressing mold is encapsulated as finished product; The anode block that it is characterized in that anode surface is generated dielectric oxide film is through dipping different viscosities conducting polymer dispersion liquid; Flood low viscous conducting polymer dispersion liquid as one deck adhesive linkage; The conducting polymer dispersion liquid of dipping viscosity higher forms the catholyte layer of capacitor, floods the surface-coated layer that full-bodied conducting polymer dispersion liquid forms solid electrolyte again; In normal temperature and hot environment, remove the dispersant in the dispersion liquid respectively; Form certain thickness conducting polymer electrolytic thin-membrane, i.e. conductive polymer cathode dielectric substrate, said dispersion liquid is by conductive polymer particles; Polymerization anion and dispersant; And surfactant, conduction reinforcing agent and binder combination form, and conductive polymer particles is that pi-conjugated conducting polymer comprises polypyrrole, polythiophene, polyaniline and polyphenylene oxide and derivative thereof; Said polymerization anion is the anion of p-methyl benzenesulfonic acid, pyrovinic acid, camphorsulfonic acid and polyphenyl alkene sulfonic acid; Dispersant is water and alcohols and derivative thereof, and the alcohols of selecting for use usually comprises methyl alcohol, ethanol, isopropyl alcohol, n-butanol; Described surfactant is a nonionic surfactant, comprises polyoxyethylene alkyl ether, polyoxyethylene glycerine fatty acid ester; Said conduction reinforcing agent comprises oxolane, N, dinethylformamide (DMF); Said adhesive comprises polyvinyl acetate, polystyrene, polyvinyl chloride; The dispersion liquid proportioning is polymer beads 0.5～10wt%, polymerization anion percetage by weight 2%～66%, activating agent 0～0.3 wt%; Reinforcing agent is 0～0.3 wt%, and adhesive is 0.03～0.3 wt%, and all the other are dispersant.
2. the manufacture method of a kind of high pressure conducting polymer electrolytic condenser according to claim 1 is characterized in that the indication polymer beads is preferred 3,4-vinyl dioxy thiophene; The preferred polystyrolsulfon acid of polymer anion (PSS); The dispersant preferred water; Surfactant also comprises ethylene propylene three alcohol fatty acid esters, polyoxyethylene fatty acid ammonia; The conduction reinforcing agent also comprises the N-methyl caprolactam, N-methyl pyrrolidone (NMP), N-octylpyrrolidone, pyrrolidones, sulfone and sulfoxide, tetramethylene sulfone, dimethyl sulfoxide (DMSO); Bonding agent also comprises Merlon, polyvinyl butyral resin, polyacrylate, polymethacrylates, polyacrylonitrile.
3. the manufacture method of a kind of high pressure conducting polymer electrolytic condenser according to claim 1; It is characterized in that low viscosity conducting polymer dispersion liquid is by conductive polymer particles; Polymer anion, dispersant, activating agent, adhesive are formed, and proportioning is conductive polymer particles 0.5～5wt%, polymer anion percetage by weight 2%～66%; Activating agent 0.01～0.3wt%; Adhesive 0.03～0.3wt%, all the other are dispersant, the viscosity of low viscosity conducting polymer dispersion liquid is 5～50mPas.
4. the manufacture method of a kind of high pressure conducting polymer electrolytic condenser according to claim 1; It is characterized in that viscosity higher conducting polymer dispersion liquid is by conductive polymer particles; Polymer anion, dispersant, reinforcing agent and adhesive are formed, and proportioning is a conductive polymer particles 1.5～10%, polymer anion percetage by weight 2%～50%; Reinforcing agent 0.01～0.3wt%; Adhesive 0.03～0.3wt%, all the other are dispersant, the viscosity of the conducting polymer dispersion liquid of viscosity higher is 8～80mPas.
5. the manufacture method of a kind of high pressure conducting polymer electrolytic condenser according to claim 1; It is characterized in that high viscosity conducting polymer dispersion liquid by conductive polymer particles, polymer anion, dispersant and adhesive are formed, and proportioning is conductive polymer particles 0.5～3wt%; Polymer anion percetage by weight 2%～55%; Adhesive 0.03～0.3wt%, all the other are dispersant, the viscosity of full-bodied conducting polymer dispersion liquid is 50～300mPas.
6. the manufacture method of a kind of high pressure conducting polymer electrolytic condenser according to claim 3; The proportioning that it is characterized in that each component of low viscosity conducting polymer dispersion liquid is: conductive polymer particles 1.5～2.5wt%; Polymer anion percetage by weight 4.7%～40%, activating agent 0.01～0.3wt%, adhesive 0.03～0.15wt%; All the other are dispersant, and the viscosity of dispersion liquid is 10～20mPas.
7. the manufacture method of a kind of high pressure conducting polymer electrolytic condenser according to claim 4; The proportioning that it is characterized in that each component of viscosity higher conducting polymer dispersion liquid is: conductive polymer particles 2.0～5wt%; Polymer anion percetage by weight 4.7%～33%, reinforcing agent 0.03～0.15wt%, adhesive 0.05～0.2wt%; All the other are dispersant, and the viscosity of dispersion liquid is 12～35mPas.
8. the manufacture method of a kind of high pressure conducting polymer electrolytic condenser according to claim 5; The proportioning that it is characterized in that each component of high viscosity conducting polymer dispersion liquid is: conductive polymer particles 1～2wt%; Polymer anion percetage by weight 4.7%～33%; Adhesive 0.05～0.2wt%, all the other are dispersant, the viscosity of full-bodied conducting polymer dispersion liquid is 70～150mPas.
9. the manufacture method of a kind of high pressure conducting polymer electrolytic condenser according to claim 1; It is characterized in that all will after removing dispersion liquid, doing dipping next time again after anode block that anode surface generates dielectric oxide film floods the conducting polymer dispersion liquid of different viscosities at every turn; Dipping low viscosity conducting polymer dispersion liquid will repeat 1～2 time; Dipping viscosity higher conducting polymer dispersion liquid will repeat 3～5 times, and dipping high viscosity conducting polymer dispersion liquid will repeat 1～2 time.
10. the manufacture method of a kind of high pressure conducting polymer electrolytic condenser according to claim 1; It is characterized in that removing the method for dispersant with room temperature volatilization and high temperature drying; The volatilization time is 0.3-2h, 50～250 ℃ of high temperature drying temperature, and be 5-40min drying time.
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