CN101350252B - Conductive polyelectrolyte polymerization liquid prescription stored in normal temperature steadily and use thereof - Google Patents
Conductive polyelectrolyte polymerization liquid prescription stored in normal temperature steadily and use thereof Download PDFInfo
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Abstract
The invention relates to a formula and an application of conducting macromolecular polymer liquid which can be steadily stored for a long time in the normal temperature, wherein the polymer liquid comprises conducting macromolecular monomers, dopant, two or more than two oxidants with different balancing anion, mixture oxidant solution which is prepared by two or more than two kinds of dissolvent with different boiling points. The polymer liquid is characterized by being steadily stored for a long time in an indoor temperature condition, and the polymerization reaction can not occur. The electrical conductivity of conducting high polymer film which is prepared by the polymer liquid is good, the equivalent series resistance is very low, and the high-temperature thermal property is stable. When the conducting high polymer film which is prepared by the polymer liquid is used as a cathode layer of a solid electrolytic capacitor, the equivalent series resistance (ESR) and the leakage current of the electrolytic capacitor can be obviously reduced, thereby the solid electrolytic capacitor with very low ESR, low leakage current and good characteristics in the high-temperature condition can be obtained.
Description
Technical field: the present invention relates to the electrolytical polymer fluid of a kind of electroconductive polymer; Particularly select for use the oxidant of solvent with different boiling and two or more structure to cooperate the solution that forms hybrid oxidant, and be applied to make the solid polymer electrolytic capacitor.
Background technology: in recent years; Along with complete electronic set is fast-developing to miniaturization, digitlization, high frequencyization, highly reliable direction; Thereby the electrolytic capacitor for one of electronic component of the high-frequency applications that is widely used in various electronic equipments has also proposed stricter requirement; In particularly high in fields such as military, space flight, aviation, weapons, boats and ships, the sophisticated electronics; Its used tantalum electrolytic capacitor is proposed the requirements at the higher level at high-frequency region Low ESRization, miniaturization, chip type and high capacity, and possessed high stability, high reliability and life-span more when hoping its work especially.At present, the high frequency chip tantalum capacitor has become one of first-selected electronic devices and components of modern military electronic equipment.
For satisfying the requirement that modern electronic technology development improves constantly the performance of electrolytic capacitor; Especially to the requirement of low impedance at high frequency; Capacitor manufacturer is carrying out fruitful groping aspect the design of tantalum electrolytic capacitor and the material, and the polymer tantalum electrolytic capacitor becomes one of final solution.This is owing to electroconductive polymer liquid electrolyte or the solid-solid inorganic salt used than the traditional electrical electrolysis condenser, like MnO
2, better electric conductivity is arranged, and have suitable high-temperature stability, so electroconductive polymer becomes the employed electrolytical exploitation trend of electrolytic capacitor of new generation.
Gerhard Hellwig, people such as Stegen at first disclose with chemical oxidative polymerization the separate matter of electroconductive polymer as capacitor for No. 4803596 at United States Patent (USP).Many subsequently companies have all carried out similar developmental research, open flat 2-130906, U.S.Pat.Nos.5,729,428 like the spy; 5,968,417; 6,001,281; Many patents such as 6,059,999 and 6,674,635 all relate to the manufacturing of electrostrictive polymer electrolysis condenser.Its main method all is after employing is flooded electroconductive polymer monomer and oxidizing agent solution (two-step method of promptly often saying) respectively with capacitor body; Make the electroconductive polymer monomer polymerization under proper condition; Remove unreacted monomer, oxidant or polymer residue through cleaning subsequently, so repeated multiple times is so that the electroconductive polymer electrolyte has enough thickness.Adopt electroconductive polymer monomer and the oxidant of this method fully to mix, therefore react inhomogeneous, and monomer and oxidizing solution intersect dipping and make the two that mutual pollution takes place again easily, bring very big difficulty to production control.Based on this shortcoming; People form polymer fluid (one-step method of promptly often saying) after with electroconductive polymer monomer, dopant, oxidant and solvent mixed together; With this polymer fluid that contains monomer and oxidant simultaneously of the fuse direct impregnation of capacitor; Subsequently under certain condition, along with the volatilization of solvent, monomer will be directly at the inner electroconductive polymer that forms of capacitor body under the effect of oxidant.One-step polymerization method has overcome monomer and oxidant undercompounding in the two-step method; The shortcoming of reaction, but generally in a single day monomer and oxidant mix, just polymerization reaction take place at once; Change the wettability of polymer fluid, make polymer fluid can't infiltrate in the hole of capacitor body.The speed of the polymer fluid polymerization reaction take place of preparing is faster simultaneously, and the employed time of polymer fluid also shortens thereupon, can cause the waste of a large amount of monomers and oxidant so in process of production, makes manufacturing cost high, can't in actual production, be applied.
People such as Philip M.Lessner are at United States Patent (USP) 6,056, and No. 089 exposure is to contain the low boiling organic compound of oxygen atom; Like oxolane, mix the formation complex compound with the ferric iron oxidant, so that the polymeric solution that electroconductive polymer monomer and oxidant are formed can be stablized preservation; But because the said compound that contains oxygen atom of this patent, like oxolane, the ability that forms complex compound with the ferric iron oxidant very a little less than; Need a large amount of use just effective, and when using in a large number, in the process of flooding repeatedly; Even if lower temperature held; Lower boiling oxolane kind solvent also is very easy to volatilization, changes the composition of polymer fluid on the one hand, on the other hand surrounding environment is also caused the pollution that has very much.This patent is used material such as the pyridine (Pyridine) that strong complexing power is arranged with iron simultaneously; But this can cause the oxidability of iron to decline to a great extent; Make in polymerization process, to obtain the very low and polymer that electric conductivity is very poor of the degree of polymerization, can't be as the electrolyte of capacitor.So it is good that the said method of this patent can't obtain high frequency characteristics, the solid electrolyte capacitators that ESR is low.In addition, reduce temperature and also help slowing down the rate of polymerization of monomer in mixed solution, for example when temperature is lower than subzero 10 ℃, even the polymerization liquid of preparation higher concentration also can stably be preserved the long period.The production environment that but will keep low temperature not only can increase the complicated degree of production, also increases the energy consumption of producing, and is difficult to realize continuous production.
Described by 3 in European patent EP-A-340 512 specifications; The solid electrolyte that 4 ethylidene dioxy thiophene are processed gathers 3; The production method of 4 ethylidene dioxy thiophene (PEDT), and the purposes that through the oxidation polymerization effect PEDT is used for the solid electrolyte of electrolytic capacitor.PEDT is as the substitute of manganese dioxide in the solid electrolytic capacitor or charge transfer complex, because it has higher conductivity, therefore can reduce the equivalent series resistance of capacitor and improve frequency performance; Flat 9-293639 number of Japan Patent; With Chinese patent CN1610027A number announcement, adopt and gather 3,4-ethene dioxythiophene (PEDT) is as electrolytical solid electrolytic capacitor; Though the polymerization rate of PEDT than other existing conducting high polymers thing (like polypyrrole; Polyaniline) polymerization rate is slower, can not stablize preservation but also fail to solve in the one-step polymerization method process polymer fluid, capacitor process high shortcoming.Therefore, make and can stablize preservation at (more than 10 ℃) under the uniform temperature condition, and the polymer fluid with very strong penetrating power being the key that one-step polymerization method is applied to actual production, also is following solid electrolytic capacitor manufacture craft Development Trend.
Summary of the invention: the purpose of this invention is to provide a kind of polymer fluid of using with one-step polymerization method making conductive solid polymer electrolyte, can not stablize the problem of preservation to solve the polymer fluid that exists in the prior art.Another object of the present invention provides the application of this polymer fluid in the polymer capacitors manufacture process.
The conducting high polymers liquid that ambient stable provided by the present invention is deposited, its Main Ingredients and Appearance comprises: (1) contains the electroconductive polymer monomer of π one conjugated polymer; (2) dopant: comprise sulfonic acid, or some other acid and its esters; (3) hybrid oxidant formed of the balance anion oxidant of two or more different structure comprises alkylbenzenesulfonate and alkylsulfonate or other hydrochlorate of transition metal; (4) mixed solvent that solvent is formed of two or more different boiling comprises low boiling ethanol and other solvent of high boiling n-butanol, and in the polymer fluid proportioning, monomer accounts for 1～8wt%; Dopant accounts for 1～1.5wt%, and oxidant accounts for 30～35wt%, and all the other are solvents, and the weight ratio between two oxidants generally is 1:1, and the proportioning between the solvent pairs is to be pressed in the mixed liquor saturated steam to be lower than 1000Pa and to be as the criterion.
Polymer fluid of the present invention can add some a small amount of assistant agents such as bonding agent (like polyvinylpyrrolidone) or coupling agent (like silane) according to different situations.
Thereby the polymer fluid that uses two kinds and above oxidant with different balance anions can in solution, suppress to make this oxidant and this solvent and electroconductive polymer monomer to be prepared each other can be stablized preservation under uniform temperature (more than 10 ℃) condition.In the capacitor fabrication process, can be provided the time of sufficient dip time and repetitive operation for capacitor body.
The oxidative polymerization of electroconductive polymer monomer is except relevant with the oxidizing potential height of monomer, and also the oxidability with oxidant has confidential relation.With monomer 3,4-ethene dioxythiophene (EDT) is an example, with regard to the oxidant that contains ferric ion; Fully confirm at present; The oxidability of ferric ion receives the balance polyanion effect on structure in the polymerization reaction, selects for use two kinds and above trivalent iron salt with different balance anions as oxidant, and two kinds of balance anions suppress each other in polymer fluid; Be formed centrally polyanion group in ferric ion being; And stoped contacting between iron ion and monomer, and reduce the oxidability of ferric ion, make the mixed solution of monomer and oxidant in room temperature or system, to keep stablizing near room temperature and low solvent.This just the present invention select for use the oxidant of two or more different balance anions to form hybrid oxidant to prepare the prerequisite that the high stability polymerization liquid is achieved.
Mostly the oxidant of iron content is solid-state (comprising p-methyl benzenesulfonic acid iron); Make the full and uniform mixing of monomer and oxidant; Just must evenly be dissolved in solid-state oxidant in the solvent earlier, adding monomer in the oxidant oxidation solution uniformly, can obtain corresponding polymer fluid then.The solvent that the present invention is used for dissolved oxidant and monomer is alcohol, ketone, water, oxolane or combination in any.In order to reduce the saturated vapour pressure of polymer fluid; What mainly need reduction is exactly the full vapour pressure of solvent; This just need comprise in solution and has higher boiling point solution composition (viscosity that this can increase solution reduces its penetrating power), simultaneously in order to improve the penetrating power of polymer fluid; Just need in mixed liquor, comprise low boiling, (this can increase the volatility of mixed liquor to the strong micromolecule solvent of permeability; Be unfavorable for that the stable of solution deposit), in order to solve the contradiction between this two, the solvent that can select to have different boiling comes the common mixed solvent of forming.Lower boiling solvent mainly can be selected the organic solvent of high volatilities such as acetone, methyl alcohol, ethanol, oxolane; The solvent of higher possibly selected isopropyl alcohol, water etc., and more high boiling solvent then can be selected dimethyl sulfoxide (DMSO) (DMSO), methyl pyrrolidone, n-butanol equal solvent.In order to improve the ratio of the electroconductive polymer product that obtains after the polymer fluid oxidation polymerization, the concentration of oxidant should reach 30wt%～35wt% in the solution, monomer concentration 1wt%-8wt%, and the best is 4wt%-6wt%.
Adopt low saturated vapor pressure mixed solvent and contain the polymer fluid that the hybrid oxidant of two kinds and above balance anion group is prepared; Can make capacitor body have sufficient dip time; Can also guarantee under the dipping of limited number of times, can obtain polyelectrolyte even compact, that electric conductivity is good, and then produce the splendid electroconductive polymer solid electrolytic capacitor of electric property.
To gather 3; It is that the chemical polymerization of oxidant is as follows shown in the reaction equation with p-methyl benzenesulfonic acid iron to 4-ethene dioxythiophene (PEDT) for example; Wherein ferric ion plays the oxidant effect; In polymerization process, being reduced into ferrous ion, is the accessory substance of reaction, need after polymerization, it be washed.Its tosylate is the balance polyanion in the polymerization process, and the toluenesulfonic acid that the process polymerization reaction forms is the dopant of polymer for this reason.
In polymer fluid prescription of the present invention, the electroconductive polymer monomer is selected from the derivative of thiophene, pyrroles, aniline or above-mentioned high polymer monomer.This thiophene is 3, the 4-ethene dioxythiophene; The percentage by weight of monomer is 1%-8% in the polymer fluid.
Oxidant is from the alkylbenzenesulfonate of transition metal or alkyl sulfonic acid (salt), to select more than one respectively in the polymer fluid prescription, and mixes this metal sulfamate (salt) more than 2 kinds.Transition metal wherein is a ferric ion, or any in the iron, copper, chromium, cerium, manganese ion.
Wherein ferric iron compound is selected from toluenesulfonic acid iron, DBSA iron, methanesulfonic acid iron, ethyl sulfonic acid iron, propane sulfonic acid iron, fourth sulfonic acid iron or its combination in any.
Solvent described in the polymer fluid prescription is from alcohols, ketone, furans or water, to select two or more solvent with different boiling to form respectively.The saturated vapor pressure of this mixed liquor is lower than 1000pa.
Wherein said oxidant in polymer fluid concentration at 30wt%～35wt%.
The said dopant of polymer fluid is selected from the salt of alkyl benzene sulphonate, alkyl sulfonic acid, sulfuric acid, phosphoric acid, citric acid or above-mentioned acid with its related derivatives, and the ratio in polymer fluid is 1～1.5%.
Because the present invention is in polymer fluid; Adopt the oxidant of two or more different balance anions to stop the oxidability of high volence metal ion, make the mixed solution of monomer and oxidant to keep stable in room temperature or near room temperature and low solvent system.Aspect solvent, experiment showed, when the use amount of low boiling point solvent is big, the bad stability of solution, the conductivity of resulting polymers is also relatively poor, suitably adds higher and high boiling solvent, can obviously improve the stability of solution.Its reason is the saturated vapor pressure that the adding of high boiling solvent has reduced polymeric solution; Make solvent in temperature-rise period; The volatilization time is longer; Help forming fine and close equal polymer membrane, but the amount of high boiling solvent is too many in solution, can causes the polymer can not complete reaction during as 80 ℃ and reduce the conductivity of production efficiency and film at lower temperature.Proportioning between high boiling solvent and the low boiling point solvent is generally 1:1～1.5.
In sum; Adopt low saturated vapor pressure mixed solvent and contain the polymer fluid that the hybrid oxidant of two kinds and above balance anion group is prepared; Can make capacitor body have sufficient dip time; Can also guarantee under the dipping of limited number of times, can obtain polyelectrolyte even compact, that electric conductivity is good, and then produce the splendid electroconductive polymer solid electrolytic capacitor of electric property.
Below in conjunction with embodiment and Comparative Examples, further specify the present invention.
Embodiment: embodiment 1
According to like following table 1 listed ratio, earlier will listed oxidant such as toluenesulfonic acid iron (III) pyrovinic acid iron (III) dissolve the formation oxidizing agent solution with solvent such as ethanol or n-butanol, with 3; 4-ethene dioxythiophene (EDT) monomer is mixed with monomer solution with solvent, then oxidizing agent solution that is prepared and monomer solution is mixed; Vibrate with ultrasonic wave; Solution is fully mixed, under room temperature (20 ℃), measure the saturated vapor pressure of mixed solution, the solution saturated steam is pressed in below the 1000Pa; And measuring the polymer fluid turbidity over time, its result is as shown in table 2.
For each polymer fluid for preparing, carry out the oxidation polymerization test by following step respectively: 1) 20 * 50mm slide is cleaned up oven dry with deionization.Treat to immerse in the polymer fluid behind the sheet glass cool to room temperature; 2) through the regular hour, take out glass substrate, in 60 ℃-80 ℃ baking oven, carry out polymerization reaction; 3) after polymerization reaction finishes,, be drying 10 minutes at 110 ℃ baking oven again with washed with de-ionized water and washed with methanol sheet glass, can be at the polymer film that obtains on glass.4) with the conductivity of PEDT film on the four point probe appearance tested glass sheet.The result is as shown in table 2 below.
Table 1
Table 2
Show that from the result of table 2 single solvent and single-oxidizer mix formed polymer fluid (filling a prescription like 1# and 2#) after preparation, the turbidity of mixed liquor rises rapidly, and the demonstration polymerization reaction is promptly carried out rapidly in solution.In fast like this polymerization liquid, capacitor body will not have enough time this mixed liquors of dipping.The same terms adopts hybrid oxidant (like 2#, 5#, 8# liquid) reaction rate slower down.The above results also shows when the low boiling point solvent use amount increases, the bad stability of solution, and the conductivity of resulting polymer is also relatively poor.Suitably adding higher and high boiling solvent such as water, butanols and NMP; Can obviously improve the stability of solution, the conductance of the polymer film of acquisition is also higher, this be because high boiling solvent volatilization time in temperature-rise period longer; Help forming fine and close polymer membrane uniformly; But when solution high boiling solvent content is too much, then can cause the polymerization reaction can not complete reaction when lower temperature (as 80 ℃), and reduce the conductivity (filling a prescription) of production efficiency and film like 9#.Therefore, obtain the polymer fluid of good stability, and the polyelectrolyte that polymerization reaction is obtained there is superior conductive capability, adopts hybrid oxidant and high low boiling point solvent to be used the effect that can obtain.
Embodiment two:
With specific volume is 50,000 μ F/g, and the tantalum powder sintering piece that is of a size of 4.3 * 3.1 * 1.1 (mm) carries out anodic oxidation in the phosphoric acid solution of 0.1wt% (percentage by weight), and wherein anodised operating voltage is 33V.Anodic oxidation is boiled and is washed and the drying and sintering piece after finishing, and forms capacitor body.With 5# formulated polymer fluid in the table 1; With above-mentioned this polymer fluid of capacitor body dipping 5min-10min; The tantalum core that will flood polymer fluid then places room temperature condition to dry about 10min, is placed in 40 ℃-60 ℃ the baking oven to react 15min, afterwards at 120 ℃ of heat treatment 10min again.With this fuse of deionized water wash 30min, in the p-methyl benzenesulfonic acid aqueous solution of 0.1wt%, anode tantalum fuse is mended formation 30 minutes, rinsing and drying in deionized water, 5 said dippings of row, drying, heat treatment and benefit forming process more afterwards again.
Then, on the half-finished conductive polymer coating that obtains, apply graphite silver slurry, carry out mold pressing then.Like this, just make and accomplished solid electrolytic capacitor.The making capacitor specific characteristics is as shown in table 3.
Embodiment three:
With the listed 8# formulated polymer fluid of table 1, with this polymer fluid of capacitor body dipping of specification such as embodiment two, by making capacitor with quadrat method, its characteristic is as shown in table 3 again.
Comparative example 1:
With the listed 2# formulated polymer fluid of table 1, contain two kinds of oxidants in the polymer fluid, but only use just alcohol of a kind of solvent.With this polymer fluid of capacitor body dipping of specification such as embodiment two, make capacitor by same step more again, its characteristic is as shown in table 3.
Comparative example 2:
With the listed 1# formulated polymer fluid of table 1, only contain single oxidant and a kind of solvent, n-butanol in the polymer fluid, with this polymer fluid of capacitor body dipping of specification such as embodiment two, make capacitor by same step more again, its characteristic is as shown in table 3.
Comparative example 3:
With the listed 4# formulated polymer fluid of table 1; Only contain a kind of oxidant methanesulfonic acid iron in the polymer fluid, but adopt mixed solvent, the capacitor body with specification such as embodiment two floods this polymer fluid again; Make capacitor by same step again, its characteristic is as shown in table 3.
Comparative example 4:
With the listed 6# formulated polymer fluid of table 1; Only contain a kind of oxidant p-methyl benzenesulfonic acid iron in the polymer fluid, but adopt mixed solvent, the capacitor body with specification such as embodiment two floods this polymer fluid again; Make capacitor by same step again, its characteristic is as shown in table 3.
Table 3
As above shown in the table 3,, can under similarity condition, produce lower ESR, low-leakage current, the good electrolytic capacitor of hot properties if adopt this method preparation polymer fluid.
The reason analysis that improves is following: compare with adopting single balance anion slaine, contain benzene sulfonamide acid group anion and the anionic two kinds of metal salt mixture of alkyl azochlorosulfonate as oxidant through employing, can improve the acidity of solution.Result's two kinds of balance anions in solution suppress each other, are formed centrally polyanion group in metal ion being, reach the effect that weakens the metal ion oxidability; And in the dipping polymerization process; The oxidant anion enters in the macromolecular structure as doping more easily, improves the degree of polymerization of conducting polymer, thereby makes the inner more all even densification of polymer of capacitor element; Reach the reduction leakage current, reduce the effect of ESR.Two kinds of balance anions generate the acid that two kinds of molecular weight vary in size respectively after through polymerization reaction, and the two forms complementary on molecular structure, and the space electric field that has improved the conducting high polymers thing distributes, and make that performance also can keep stable under its hot conditions.
Claims (8)
1. conductive polyelectrolyte polymer fluid that ambient stable is deposited, it is characterized in that main component comprises: (1) contains the electroconductive polymer monomer of pi-conjugated polymer; (2) dopant: comprise sulfonic acid or some other acid and its esters; The hybrid oxidant that the balance anion oxidant of (3) two kinds of different structures is formed comprises the alkylbenzenesulfonate and the alkylsulfonate of transition metal; (4) mixed solvent that solvent is formed of two or more different boiling comprises low boiling point solvent ethanol, methyl alcohol or acetone and high boiling solvent n-butanol, methyl pyrrolidone or dimethyl sulfoxide (DMSO), and in the polymer fluid proportioning, monomer accounts for 1～8wt%; Dopant accounts for 1～1.5wt%; Oxidant accounts for 30～35wt%; All the other are mixed solvents, and the weight ratio between the hybrid oxidant is 1: 1, and the proportioning between the mixed solvent is to be lower than 1000Pa with the mixed solvent saturated vapor pressure to be as the criterion; Higher boiling point and low boiling point solvent proportioning are 1: 1～1.5, and some other acid is meant sulfuric acid, phosphoric acid or citric acid.
2. the conductive polyelectrolyte polymer fluid that a kind of ambient stable according to claim 1 is deposited is characterized in that the electroconductive polymer monomer is selected from the derivative of thiophene, pyrroles, aniline or above-mentioned high polymer monomer, and the ratio in polymer fluid is 4～6wt%.
3. the conductive polyelectrolyte polymer fluid that a kind of ambient stable according to claim 2 is deposited is characterized in that the derivative of thiophene is meant 3, the 4-ethene dioxythiophene, and the ratio in polymer fluid accounts for 5wt%.
4. the conductive polyelectrolyte polymer fluid that a kind of ambient stable according to claim 1 is deposited; It is characterized in that oxidant is meant the alkylbenzenesulfonate or the alkylsulfonate of any transition metal ions in ferric ion or copper, chromium or the manganese, and from its alkylbenzenesulfonate or alkylsulfonate, respectively select a kind of or two kinds cooperate.
5. the conductive polyelectrolyte polymer fluid that a kind of ambient stable according to claim 4 is deposited; The alkylbenzenesulfonate or the alkylsulfonate that it is characterized in that ferric ion are selected from benzene sulfonic acid iron, DBSA iron, methanesulfonic acid iron, ethyl sulfonic acid iron, propane sulfonic acid iron, fourth sulfonic acid iron or its combination in any.
6. the conductive polyelectrolyte polymer fluid of depositing according to claim 1 or 2 or 3 or 4 or 5 described a kind of ambient stables is characterized in that dopant is selected from the salt and the related derivatives thereof of alkyl benzene sulphonate, alkyl sulfonic acid, sulfuric acid, phosphoric acid, citric acid or above-mentioned acid.
7. the conductive polyelectrolyte polymer fluid that a kind of ambient stable according to claim 1 is deposited, its characteristic add polyvinylpyrrolidone bonding agent or coupling agent silane in polymer fluid.
8. the conductive polyelectrolyte polymer fluid that a kind of ambient stable according to claim 1 is deposited, thus it is characterized in that polymer fluid is used to flood the porousness sintered body manufacturing solid electrolytic capacitor of solid electrolytic capacitor anode.
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| CN102709055B (en) * | 2012-06-11 | 2015-09-02 | 中国振华（集团）新云电子元器件有限责任公司 | A kind of conducting high polymers thing catholyte solution and Synthesis and applications thereof |
| 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 |
| CN104211969B (en) * | 2014-09-10 | 2017-02-01 | 万星光电子(东莞)有限公司 | Preparation method of PEDOT/PSS dispersion liquid and preparation method of high pressure solid capacitor |
| CN105111416B (en) * | 2015-09-22 | 2017-08-04 | 东莞市富默克化工有限公司 | A kind of plated conductive polymer and preparation method thereof |
| CN106811009A (en) * | 2017-01-25 | 2017-06-09 | 新应材股份有限公司 | Conductive polymer composites solution and its antistatic film and flat-panel screens |
| KR102414097B1 (en) * | 2017-05-31 | 2022-06-27 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Method for manufacturing conductive polymer solid electrolytic capacitor and conductive polymer |
| CN108695497A (en) * | 2018-05-03 | 2018-10-23 | 重庆工商大学 | A kind of preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery |
| CN112979927B (en) * | 2019-12-17 | 2021-12-14 | 深圳新宙邦科技股份有限公司 | Composition, polymer for capacitor and capacitor |
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