CN110003496B - Preparation method of polymer dispersion and polymer dispersion - Google Patents
Preparation method of polymer dispersion and polymer dispersion Download PDFInfo
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- CN110003496B CN110003496B CN201811145160.XA CN201811145160A CN110003496B CN 110003496 B CN110003496 B CN 110003496B CN 201811145160 A CN201811145160 A CN 201811145160A CN 110003496 B CN110003496 B CN 110003496B
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- 239000004815 dispersion polymer Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003990 capacitor Substances 0.000 claims abstract description 84
- 239000007787 solid Substances 0.000 claims abstract description 72
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000007800 oxidant agent Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229920000123 polythiophene Polymers 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 229920000767 polyaniline Polymers 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 3
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 abstract description 8
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 description 25
- 238000005259 measurement Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000000265 homogenisation Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- FLIOATBXVNLPLK-UHFFFAOYSA-N 3-amino-4-methoxybenzenesulfonic acid Chemical compound COC1=CC=C(S(O)(=O)=O)C=C1N FLIOATBXVNLPLK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- IEIWNKOVMOXPAO-UHFFFAOYSA-M sodium;2-amino-5-methoxybenzenesulfonate Chemical compound [Na+].COC1=CC=C(N)C(S([O-])(=O)=O)=C1 IEIWNKOVMOXPAO-UHFFFAOYSA-M 0.000 description 1
- GLXWXYTYBIBBLD-UHFFFAOYSA-M sodium;3-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=CC(S([O-])(=O)=O)=C1 GLXWXYTYBIBBLD-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
In order to overcome the problems that the capacity extraction rate of a solid electrolytic capacitor is easy to rapidly decrease and the ESR value is rapidly increased in the cyclic charge-discharge process of a polymer dispersion obtained by doping a conventional doping agent in the prior art, the invention provides a preparation method of the polymer dispersion, which comprises the following steps: s1, under an inert atmosphere, enabling the monomer to contact with an oxidant for reaction to obtain a first conductive polymer; s2, the first conductive polymer is brought into contact with the second conductive polymer in a solvent to obtain a polymer dispersion. Meanwhile, the invention also discloses the polymer dispersion prepared by the method. The polymer dispersion prepared by the method provided by the invention has high conductivity, and the solid electrolytic capacitor prepared by the method has good stability and long service life, and does not have the problems of rapid reduction of capacity extraction rate and rapid increase of ESR value.
Description
Technical Field
The invention relates to the field of conductive high molecular materials, in particular to a preparation method of a polymer dispersion and the polymer dispersion prepared by the method.
Background
The solid electrolytic capacitor adopts a solid conductive material with high conductivity and good thermal stability as an electrolyte, and compared with the common electrolytic capacitor, the solid electrolytic capacitor not only has all the characteristics of the common electrolytic capacitor, but also has the characteristics of good reliability, long service life, high frequency, low impedance, super-large ripple current resistance and the like, and can overcome the defects of easy liquid leakage and short service life of a liquid electrolytic capacitor. With the rapid development of the domestic electronic information industry, from the development trend in recent years, the solid electrolytic capacitor will gradually replace the common low-voltage electrolytic capacitor and become one of the post products of the electronic information industry in the 21 st century.
With the improvement of the performance requirements of solid electrolytic capacitors, the electrical conductivity of the conductive polymer electrolyte is further improved, so that the ESR value of the capacitor is a common pursuit of researchers. Doping is an effective way to improve the conductivity of polymers, and high molecular materials with conjugated chemical double bonds can be oxidized or reduced by adding a dopant to obtain better electrochemical activity. The purposes of reducing the energy band gap and reducing the migration resistance of free charges are achieved through doping, so that the conductivity of the conjugated polymer is remarkably improved, and the conductivity can be improved by several to tens of orders of magnitude. The conjugated structure of the polymer enables large pi electrons to have higher electron mobility and high electron delocalization degree. The current doping method generally introduces a certain dopant (such as elementary iodine, ferric chloride, etc.) into a polymer system, and due to the low electron dissociation property, the dopant can lose or partially lose electrons to be oxidized, so that P-type doping occurs; and because of good electron affinity, electrons can be obtained or partially obtained to be reduced, and n-type doping occurs, so that the conductivity of the polymer is improved. For example, in the prior art, a conductive polymer material is often doped with a dopant such as polystyrene sulfonic acid to improve conductivity.
However, the conventional dopant and conjugated polymer have poor compatibility and dispersibility, which hinder charge transfer and conductivity improvement. Moreover, it is particularly important that, after the polymer dispersion doped with the dopant commonly used at present is used in the solid electrolytic capacitor, the capacity extraction rate of the solid electrolytic capacitor is rapidly reduced and the ESR value is rapidly increased during the charging and discharging processes, so that the performance of the solid electrolytic capacitor is rapidly deteriorated and the solid electrolytic capacitor is failed.
Disclosure of Invention
The invention aims to solve the technical problems that the capacity extraction rate of a solid electrolytic capacitor is easy to rapidly decrease and the ESR value is easy to rapidly increase in the cyclic charge and discharge process of a polymer dispersion obtained by doping with a conventional doping agent in the prior art, and provides a preparation method of the polymer dispersion and the polymer dispersion prepared by the method.
The technical scheme adopted by the invention for solving the technical problems is as follows:
there is provided a process for preparing a polymer dispersion comprising the steps of:
s1, under an inert atmosphere, enabling the monomer to contact with an oxidant for reaction to obtain a first conductive polymer;
s2, contacting the first conductive polymer with the second conductive polymer in a solvent to obtain a polymer dispersion;
the monomer in the step S1 is selected from one or more compounds with the following general formula:
wherein R represents H or at least one of optionally substituted linear or branched C1-C18 alkyl, optionally substituted C5-C12 cycloalkyl, optionally substituted C6-C14 aryl, optionally substituted C7-C18 aralkyl, optionally substituted C1-C4 hydroxyalkyl or hydroxyl;
a represents one of a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group;
y represents one of NH and S;
n is an integer of 1 to 8;
x is selected from CO2、SO3One of (1);
z is hydrogen or Na.
Further, before the step S1, dissolving a monomer in a solvent to obtain a monomer solution; the solvent is water.
Further, in step S1, the oxidizing agent is one or more selected from potassium persulfate, sodium persulfate, ammonium persulfate, ferric sulfate, hydrogen peroxide, and potassium permanganate.
Further, in the step S1, the monomer is in contact reaction with an oxidant in a solvent environment; the solvent is water.
Further, in the step S1, the molar ratio of the monomer to the oxidant is 1:0.1-1: 8.
Further, the reaction temperature in the step S1 is 10-40 ℃.
Further, in step S1, the inert atmosphere is a nitrogen atmosphere.
Further, in step S2, the second conductive polymer is selected from one or more of polythiophene, polypyrrole, and polyaniline.
Further, in the step S2, the molar ratio of the first conductive polymer to the second conductive polymer is 1:0.5-1: 6.
Further, the solvent in step S2 is water.
Meanwhile, the invention also provides the polymer dispersion prepared by the method.
In the method provided by the invention, a first conductive polymer is obtained by carrying out oxidative polymerization on a specific monomer, and then the first conductive polymer and a second conductive polymer are mixed and reacted to obtain a polymer dispersion. Because the monomer adopted by the reaction is a specific aniline or thiophene monomer containing a carboxylic acid group, a sulfonic acid group or a phosphoric acid group, the first conductive polymer obtained by the polymerization of the monomer reacts with the second conductive polymer, and is combined with the second conductive polymer in a chemical bond form, the compatibility and the dispersibility are good, and the migration efficiency of charges on an interface can be effectively improved, so that the conductivity is improved; importantly, the monomer contains carboxylic acid group, sulfonic group or phosphoric acid group, and the first conducting polymer and the second conducting polymer are mixed and reacted, so that functional groups which play main roles in the obtained polymer dispersion are combined through chemical bonds, and the polymer dispersion is firmer.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation method of the polymer dispersion provided by the invention comprises the following steps:
s1, under an inert atmosphere, enabling the monomer to contact with an oxidant for reaction to obtain a first conductive polymer;
s2, contacting the first conductive polymer with the second conductive polymer in a solvent to obtain a polymer dispersion;
the monomer in the step S1 is selected from one or more compounds with the following general formula:
wherein R represents H or at least one of optionally substituted linear or branched C1-C18 alkyl, optionally substituted C5-C12 cycloalkyl, optionally substituted C6-C14 aryl, optionally substituted C7-C18 aralkyl, optionally substituted C1-C4 hydroxyalkyl or hydroxyl;
a represents one of a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group;
y represents one of NH and S;
n is an integer of 1 to 8;
x is selected from CO2、SO3One of (1);
z is hydrogen or Na.
Specifically, the monomer in step S1 may be dissolved in a solvent to obtain a monomer solution, which is convenient for operation and control of the reaction process. As known to those skilled in the art, the solvent used in each step of the present invention may be water.
The monomer used in the present invention is at least an aniline monomer containing a carboxylic acid group, a sulfonic acid group or a phosphoric acid group or a monomer containing CO, as described above2、SO3Thiophene monomer (b) of (a). The particular type of monomer can be selected by one skilled in the art as desired.
As described above, in step S1, the monomer is brought into contact with the oxidizing agent in an inert atmosphere to react with the oxidizing agent, thereby obtaining the first conductive polymer.
The inert gas atmosphere is an atmosphere known in the field of chemical reaction, and for example, a nitrogen gas atmosphere can be used.
The reaction of the monomer and the oxidizing agent may be carried out in a solvent atmosphere, and for example, the monomer solution may be mixed with an oxidizing agent solution containing the oxidizing agent (the solvent may be water) to react the monomer and the oxidizing agent.
In the invention, the oxidant is selected from one or more of potassium persulfate, sodium persulfate, ammonium persulfate, ferric sulfate, hydrogen peroxide and potassium permanganate.
In step S1, the molar ratio of the monomer to the oxidant is determined according to the specific types of the monomer and the oxidant, and the relative amounts of the two can be determined by those skilled in the art according to the common general knowledge. In the present invention, it is preferable that the molar ratio of the monomer to the oxidizing agent in the step S1 is 1:0.1 to 1: 5.
The reaction in step S1 may be performed at normal temperature, for example, the reaction temperature in step S1 is 10-40 ℃.
The first conductive polymer having a specific structure can be obtained by the reaction in step S1. According to the present invention, the polymer dispersion of the present invention is obtained by mixing a solution containing the first conductive polymer with a solution containing the second conductive polymer to react the first conductive polymer with the second conductive polymer.
In step S2, the second conductive polymer is one or more selected from polythiophene, polypyrrole, and polyaniline.
Further, in step S2, the relative content between the first conductive polymer and the second conductive polymer may vary widely, and the molar ratio of the first conductive polymer to the second conductive polymer is preferably 1:0.5-1: 4.
Further, the solvent in step S2 is water.
Meanwhile, the invention also provides the polymer dispersion prepared by the method.
The present invention will be further illustrated by the following examples.
Example 1
This example illustrates the preparation of the polymer dispersion disclosed in the present invention, and a solid electrolytic capacitor prepared using the dispersion.
The components of the formula of the embodiment are respectively added according to the following parts: 150g of pure water and 2.56g of sulfanilic acid, 2.04g of hydrogen peroxide is used as an oxidant, the reaction temperature is 20 ℃, the reaction time is 20 hours, the product and the aqueous polythiophene dispersion are subjected to blending reaction and then to homogenization treatment, and the molar ratio of the product to the aqueous polythiophene dispersion is 1: 2.
Then, the core package of the solid electrolytic capacitor is immersed in the polymer dispersion for 30min under the condition of negative pressure and dried, the steps are repeated for 3 times, and then the solid electrolytic capacitor is assembled by sealing.
The electrostatic capacity, loss value and equivalent series resistance of the capacitor were tested using an automated electronic parts analyzer in a manner that referenced conventional measurements of solid electrolytic capacitors, not to be described herein.
And then, under the condition of 1.15 times of rated voltage, the solid electrolytic capacitor is charged for 3 seconds and then discharged for 3 seconds, the cycle is repeated for 1000 times, and the electrostatic capacity, the loss value and the equivalent series resistance of the solid electrolytic capacitor are tested again.
The test results are shown in table 1.
Example 2
This example illustrates the preparation of the polymer dispersion disclosed in the present invention, and a solid electrolytic capacitor prepared using the dispersion.
The process and measurement in this example are essentially the same as in example 1, except that: 160g of pure water and 2.73g of o-aminobenzenesulfonic acid, 2.53g of potassium persulfate is used as an oxidant, the reaction temperature is 25 ℃, the reaction time is 23 hours, the product and the polythiophene aqueous dispersion are subjected to blending reaction and then are subjected to homogenization treatment, and the molar ratio of the product to the polythiophene aqueous dispersion is 1: 1.
Then, the core package of the solid electrolytic capacitor is immersed in the polymer dispersion for 30min under the condition of negative pressure and dried, the steps are repeated for 3 times, and then the solid electrolytic capacitor is assembled by sealing.
The electrostatic capacity, loss value and equivalent series resistance of the capacitor were tested using an automated electronic parts analyzer in a manner that referenced conventional measurements of solid electrolytic capacitors, not to be described herein.
And then, under the condition of 1.15 times of rated voltage, the solid electrolytic capacitor is charged for 3 seconds and then discharged for 3 seconds, the cycle is repeated for 1000 times, and the electrostatic capacity, the loss value and the equivalent series resistance of the solid electrolytic capacitor are tested again.
The test results are shown in table 1.
Example 3
This example illustrates the preparation of the polymer dispersion disclosed in the present invention, and a solid electrolytic capacitor prepared using the dispersion.
The process and measurement in this example are essentially the same as in example 1, except that: 168g of pure water and 2.41g of sodium m-aminobenzenesulfonate, 2.33g of sodium persulfate is used as an oxidant, the reaction temperature is 18 ℃, the reaction time is 26 hours, the product and the polyaniline aqueous dispersion are subjected to blending reaction and then to homogenization treatment, and the molar ratio of the product to the polyaniline aqueous dispersion is 1: 3.
Then, the core package of the solid electrolytic capacitor is immersed in the polymer dispersion for 30min under the condition of negative pressure and dried, the steps are repeated for 3 times, and then the solid electrolytic capacitor is assembled by sealing.
The electrostatic capacity, loss value and equivalent series resistance of the capacitor were tested using an automated electronic parts analyzer in a manner that referenced conventional measurements of solid electrolytic capacitors, not to be described herein.
And then, under the condition of 1.15 times of rated voltage, the solid electrolytic capacitor is charged for 3 seconds and then discharged for 3 seconds, the cycle is repeated for 1000 times, and the electrostatic capacity, the loss value and the equivalent series resistance of the solid electrolytic capacitor are tested again.
The test results are shown in table 1.
Example 4
This example illustrates the preparation of the polymer dispersion disclosed in the present invention, and a solid electrolytic capacitor prepared using the dispersion.
The process and measurement in this example are essentially the same as in example 1, except that: 180g of pure water and 3.61g of 3-amino-4-methoxybenzenesulfonic acid, 2.51g of ammonium persulfate is used as an oxidant, the reaction temperature is 26 ℃, the reaction time is 21h, the product and polypyrrole powder are subjected to blending reaction and then are subjected to homogenization treatment, and the molar ratio of the product to the polypyrrole powder is 1: 0.5.
Then, the core package of the solid electrolytic capacitor is immersed in the polymer dispersion for 30min under the condition of negative pressure and dried, the steps are repeated for 3 times, and then the solid electrolytic capacitor is assembled by sealing.
The electrostatic capacity, loss value and equivalent series resistance of the capacitor were tested using an automated electronic parts analyzer in a manner that referenced conventional measurements of solid electrolytic capacitors, not to be described herein.
And then, under the condition of 1.15 times of rated voltage, the solid electrolytic capacitor is charged for 3 seconds and then discharged for 3 seconds, the cycle is repeated for 1000 times, and the electrostatic capacity, the loss value and the equivalent series resistance of the solid electrolytic capacitor are tested again.
The test results are shown in table 1.
Example 5
This example illustrates the preparation of the polymer dispersion disclosed in the present invention, and a solid electrolytic capacitor prepared using the dispersion.
The process and measurement in this example are essentially the same as in example 1, except that: 143g of pure water and 1.63g of sodium metanilic sulfonate, 5.04g of ferric sulfate is used as an oxidant, the reaction temperature is 15 ℃, the reaction time is 10 hours, the product and the aqueous polythiophene dispersion are subjected to blending reaction and then are subjected to homogenization treatment, and the molar ratio of the product to the aqueous polythiophene dispersion is 1: 4.
Then, the core package of the solid electrolytic capacitor is immersed in the polymer dispersion for 30min under the condition of negative pressure and dried, the steps are repeated for 3 times, and then the solid electrolytic capacitor is assembled by sealing.
The electrostatic capacity, loss value and equivalent series resistance of the capacitor were tested using an automated electronic parts analyzer in a manner that referenced conventional measurements of solid electrolytic capacitors, not to be described herein.
And then, under the condition of 1.15 times of rated voltage, the solid electrolytic capacitor is charged for 3 seconds and then discharged for 3 seconds, the cycle is repeated for 1000 times, and the electrostatic capacity, the loss value and the equivalent series resistance of the solid electrolytic capacitor are tested again.
The test results are shown in table 1.
Example 6
This example illustrates the preparation of the polymer dispersion disclosed in the present invention, and a solid electrolytic capacitor prepared using the dispersion.
The process and measurement in this example are essentially the same as in example 1, except that: 170g of pure water and 2.32g of sodium 2-amino-5-methoxybenzenesulfonate, 1.51g of potassium permanganate is used as an oxidant, the reaction temperature is 35 ℃, the reaction time is 30 hours, the product and the polyaniline aqueous dispersion are subjected to blending reaction and then to homogenization treatment, and the molar ratio of the product to the polyaniline aqueous dispersion is 1: 1.
Then, the core package of the solid electrolytic capacitor is immersed in the polymer dispersion for 30min under the condition of negative pressure and dried, the steps are repeated for 3 times, and then the solid electrolytic capacitor is assembled by sealing.
The electrostatic capacity, loss value and equivalent series resistance of the capacitor were tested using an automated electronic parts analyzer in a manner that referenced conventional measurements of solid electrolytic capacitors, not to be described herein.
And then, under the condition of 1.15 times of rated voltage, the solid electrolytic capacitor is charged for 3 seconds and then discharged for 3 seconds, the cycle is repeated for 1000 times, and the electrostatic capacity, the loss value and the equivalent series resistance of the solid electrolytic capacitor are tested again.
The test results are shown in table 1.
Example 7
This example illustrates the preparation of the polymer dispersion disclosed in the present invention, and a solid electrolytic capacitor prepared using the dispersion.
The process and measurement in this example are essentially the same as in example 1, except that: 190g of pure water and 2.63g of o-aminobenzenesulfonic acid, 4.12g of ammonium persulfate is used as an oxidant, the reaction temperature is 10 ℃, the reaction time is 24 hours, the product and the polythiophene aqueous dispersion are subjected to blending reaction and then are subjected to homogenization treatment, and the molar ratio of the product to the polythiophene aqueous dispersion is 1: 3.
Then, the core package of the solid electrolytic capacitor is immersed in the polymer dispersion for 30min under the condition of negative pressure and dried, the steps are repeated for 3 times, and then the solid electrolytic capacitor is assembled by sealing.
The electrostatic capacity, loss value and equivalent series resistance of the capacitor were tested using an automated electronic parts analyzer in a manner that referenced conventional measurements of solid electrolytic capacitors, not to be described herein.
And then, under the condition of 1.15 times of rated voltage, the solid electrolytic capacitor is charged for 3 seconds and then discharged for 3 seconds, the cycle is repeated for 1000 times, and the electrostatic capacity, the loss value and the equivalent series resistance of the solid electrolytic capacitor are tested again.
The test results are shown in table 1.
Example 8
This example illustrates the preparation of the polymer dispersion disclosed in the present invention, and a solid electrolytic capacitor prepared using the dispersion.
The process and measurement in this example are essentially the same as in example 1, except that: 180g of pure water and 3.15g of sulfanilic acid, 2.57g of sodium persulfate is used as an oxidant, the reaction temperature is 40 ℃, the reaction time is 20 hours, the product and the polyaniline aqueous dispersion are subjected to blending reaction and then to homogenization treatment, and the molar ratio of the product to the polyaniline aqueous dispersion is 1: 4.
Then, the core package of the solid electrolytic capacitor is immersed in the polymer dispersion for 30min under the condition of negative pressure and dried, the steps are repeated for 3 times, and then the solid electrolytic capacitor is assembled by sealing.
The electrostatic capacity, loss value and equivalent series resistance of the capacitor were tested using an automated electronic parts analyzer in a manner that referenced conventional measurements of solid electrolytic capacitors, not to be described herein.
And then, under the condition of 1.15 times of rated voltage, the solid electrolytic capacitor is charged for 3 seconds and then discharged for 3 seconds, the cycle is repeated for 1000 times, and the electrostatic capacity, the loss value and the equivalent series resistance of the solid electrolytic capacitor are tested again.
The test results are shown in table 1.
Comparative example 1
This comparative example is intended to illustrate by comparison the process for preparing the polymer dispersion disclosed herein, and the solid electrolytic capacitor prepared using the dispersion.
The solid electrolytic capacitor core package is soaked in the conventional PEDOT/PSS aqueous dispersion under the vacuum condition for 30min, then is baked in an oven at 125 ℃ for 30min, and the steps are repeated for 3 times. And then the solid electrolytic capacitor is obtained through sealing and assembling.
The electrostatic capacity, loss value and equivalent series resistance of the solid electrolytic capacitor were tested using an automatic electronic parts analyzer. And then, under the condition of 1.15 times of rated voltage, the solid electrolytic capacitor is charged for 3 seconds and then discharged for 3 seconds, the cycle is repeated for 1000 times, and the electrostatic capacity, the loss value and the equivalent series resistance of the solid electrolytic capacitor are tested again.
The test results of the above examples and comparative examples are shown in table 1 below:
TABLE 1 solid aluminium electrolytic capacitor various performance test results (16V 1000. mu.F core package)
As can be seen from the data in Table 1, the solid electrolytic capacitor prepared from the polymer dispersion provided by the invention has low capacity attenuation rate after cyclic charge and discharge, and the maximum attenuation rate is only-2.5%; in the comparative example, the solid electrolytic capacitor prepared by the conventional PEDOT/PSS aqueous dispersion has a large capacity attenuation rate of-21.0% after cyclic charge and discharge, which shows that the polymer dispersion of the invention basically has no dedoping phenomenon after repeated charge and discharge, and the polymer dispersion has excellent stability, thereby ensuring the performance stability of the solid electrolytic capacitor and greatly prolonging the service life of the solid electrolytic capacitor.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method of preparing a polymer dispersion comprising the steps of:
s1, under an inert atmosphere, enabling the monomer to contact with an oxidant for reaction to obtain a first conductive polymer;
s2, contacting the first conductive polymer with the second conductive polymer in a solvent to obtain a polymer dispersion;
the monomer in the step S1 is selected from one or more compounds with the following general formula:
wherein R represents H or at least one of optionally substituted linear or branched C1-C18 alkyl, optionally substituted C5-C12 cycloalkyl, optionally substituted C6-C14 aryl, optionally substituted C7-C18 aralkyl, optionally substituted C1-C4 hydroxyalkyl or hydroxyl;
a represents one of a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group;
y represents one of NH and S;
n is an integer of 1 to 8;
x is selected from CO2、SO3One of (1);
z is hydrogen or Na;
in step S2, the second conductive polymer is selected from one or more of polythiophene, polypyrrole, and polyaniline.
2. The method according to claim 1, wherein the step S1 is preceded by dissolving the monomer in a solvent to obtain a monomer solution;
the solvent is water.
3. The method according to claim 1, wherein in step S1, the oxidant is one or more selected from potassium persulfate, sodium persulfate, ammonium persulfate, ferric sulfate, hydrogen peroxide, and potassium permanganate.
4. The method according to claim 1, wherein in step S1, the monomer is contacted with an oxidant in a solvent environment for reaction;
the solvent is water.
5. The method according to claim 1, wherein in step S1, the molar ratio of the monomer to the oxidizing agent is 1:0.1-1: 8.
6. The production method according to any one of claims 1 to 5, wherein the reaction temperature in the step S1 is 10 to 40 ℃.
7. The method according to claim 1, wherein in step S1, the inert gas atmosphere is a nitrogen gas atmosphere.
8. The production method according to any one of claims 1 to 5 or 7, wherein in step S2, the molar ratio of the first conductive polymer to the second conductive polymer is 1:0.5 to 1: 6.
9. A polymer dispersion produced by the method of any one of claims 1 to 8.
10. A solid electrolytic capacitor comprising the polymer dispersion of claim 9.
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| US5284723A (en) * | 1989-07-14 | 1994-02-08 | Solvay & Cie (Societe Anonyme) | Electrochemical energy storage devices comprising electricaly conductive polymer and their uses |
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