CN110010353A - A kind of polymeric dispersions and solid electrolytic capacitor - Google Patents
A kind of polymeric dispersions and solid electrolytic capacitor Download PDFInfo
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- CN110010353A CN110010353A CN201811151153.0A CN201811151153A CN110010353A CN 110010353 A CN110010353 A CN 110010353A CN 201811151153 A CN201811151153 A CN 201811151153A CN 110010353 A CN110010353 A CN 110010353A
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- electrolytic capacitor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
Abstract
Decline rapidly to overcome polymeric dispersions in the prior art to easily lead to solid electrolytic capacitor capacity extraction rate during cycle charge-discharge, the problem of ESR value increases rapidly, the present invention provides a kind of polymeric dispersions, including solvent and the first conducting polymer and the second conducting polymer that are scattered in solvent；First conducting polymer is polymerize to obtain by specific compound, and second conducting polymer is selected from one of polythiophene, polypyrrole, polyaniline or a variety of.The present invention also provides the solid electrolytic capacitors being prepared by the polymeric dispersions.Polymeric dispersions conductivity provided by the invention is high, and the solid electrolytic capacitor stability thus prepared is good, long service life, is not in that capacity extraction rate declines rapidly and the problem of ESR value increases rapidly.
Description
Technical field
The present invention relates to conductive polymer material field, more particularly to a kind of preparation method of polymeric dispersions, with
And the polymeric dispersions using this method preparation.
Background technique
The solid conductive material that solid electrolytic capacitor is high using conductivity, thermal stability is good is and common as electrolyte
Electrolytic capacitor is compared, it not only has all characteristics of general electrolytic capacitor, and have good reliability, long service life,
The characteristics such as low impedance at high frequency, resistance to especially big ripple current, and liquid electrolyte capacitor can be overcome to be easy leakage, service life short disadvantage
End.With the rapid development of domestic electronics and information industry, from the point of view of development trend in recent years, solid electrolytic capacitor will gradually
Substitute pressure common electrolytic capacitor, and one of the pillar product that 21 century electronics and information industry will be become.
Raising with people to solid electrolytic capacitor performance requirement further increases the electrolysis of conducting high polymers object
Matter conductivity, so that reducing capacitor ESR value becomes the target that researcher pursues jointly.Doping is to improve polymer conductivity
A kind of effective way, the high molecular material with chemical conjugate double bond can be easily oxidized or reduced by the way that dopant is added to obtain
Obtain better electro-chemical activity.By adulterating the migration resistance for achieving the purpose that reduction band gap and reducing free charge, thus
The electric conductivity of conjugated polymer is significantly improved, several to more than ten order of magnitude can be improved in conductivity.The conjugated structure of polymer, makes
Big pi-electron electron mobility with higher is obtained, electron delocalization degree is high.Current doping method is usually by certain dopant
(such as iodine, iron chloride) is introduced into polymeric system, since its electron dissociation is lower, can lose or part loses electronics
And be oxidized, p-type doping occurs；Again because of its own good electron affinity, available or part obtains electronics and is gone back
Original occurs n-type doping, the conductivity of polymer is caused to improve.For example, mostly using polystyrolsulfon acid etc. to mix greatly in the prior art
Miscellaneous dose is doped conductive polymer material, to improve conductivity.
But currently used dopant and conjugated polymer the problems such as there are poor compatibilities, poor dispersion, it hinders
The transmission of charge and the raising of conductivity.Also, particular, it is important that the polymerization after being adulterated by currently used dopant
Object dispersion is used for after solid electrolytic capacitor, and in charge and discharge process, solid electrolytic capacitor capacity extraction rate can be rapid
Decline, ESR value are increased rapidly, are failed so as to cause solid electrolytic capacitor performance rapid degradation.
Summary of the invention
The technical problem to be solved by the present invention is to easily lead to solid state electrolysis for polymeric dispersions in the prior art
The problem of condenser capacity extraction rate declines rapidly, and ESR value increases rapidly provides a kind of polymeric dispersions, and using should
The solid electrolytic capacitor that polymeric dispersions are prepared.
It is as follows that the present invention solves technical solution used by above-mentioned technical problem:
A kind of polymeric dispersions are provided, are led including solvent and the first conducting polymer being scattered in solvent and second
Electric macromolecule；
First conducting polymer is by selected from having one of following general formula compound represented or a variety of polymerize
It arrives:
Wherein, R indicates H or the linear chain or branched chain C1-C18 alkyl optionally replaced, the C5-C12 naphthenic base optionally replaced, appoints
The C6-C14 aryl for choosing generation, the C7-C18 aralkyl optionally replaced, in the C1-C4 hydroxy alkyl or hydroxyl that optionally replace extremely
Few one kind；
A indicates one of carboxylic acid group, sulfonic group or phosphate；
Y indicates one of NH, S；
N is the integer of 1-8；
X is selected from CO2、SO3One of；
Z is hydrogen or Na；
Second conducting polymer is selected from one of polythiophene, polypyrrole, polyaniline or a variety of.
Further, the molar ratio of first conducting polymer and the second conducting polymer is 1:0.5-1:6.
Further, the solvent is selected from water, ethyl alcohol.One of or it is a variety of.
Further, the average grain diameter of the first conducting polymer is 20-150nm in the polymeric dispersions.
Further, the average grain diameter of the second conducting polymer is 10-100nm in the polymeric dispersions.
Meanwhile the present invention also provides a kind of solid electrolytic capacitor, including core packet, the core packet includes successively being spaced to set
Anode, the first diaphragm, cathode, the second diaphragm set；The anode surface is attached with dielectric layer, and the dielectric layer surface is attached
Have a conductive polymer coating, the first conducting polymer and the second conducting polymer are contained in the conductive polymer coating；
First conducting polymer is by selected from having one of following general formula compound represented or a variety of polymerize
It arrives:
Wherein, R indicates H or the linear chain or branched chain C1-C18 alkyl optionally replaced, the C5-C12 naphthenic base optionally replaced, appoints
The C6-C14 aryl for choosing generation, the C7-C18 aralkyl optionally replaced, in the C1-C4 hydroxy alkyl or hydroxyl that optionally replace extremely
Few one kind；
A indicates one of carboxylic acid group, sulfonic group or phosphate；
Y indicates one of NH, S；
N is the integer of 1-8；
X is selected from CO2、SO3One of；
Z is hydrogen or Na；
Second conducting polymer is selected from one of polythiophene, polypyrrole, polyaniline or a variety of.
Further, the conductive polymer coating with a thickness of 100-200 μm.
Further, the average grain diameter of the first conducting polymer is 20-150nm in the conductive polymer coating.
Further, the average grain diameter of the second conducting polymer is 10-100nm in the conductive polymer coating.
Further, the molar ratio of the first conducting polymer and the second conducting polymer is 1 in the conductive polymer coating:
0.5-1:6。
Further, the solid electrolytic capacitor is solid-state aluminum electrolytic capacitor or solid-state tantalum electrolytic capacitor.
Polymeric dispersions provided by the invention include the first conducting polymer and the second conducting polymer, especially first
Conducting polymer is by selected from one of aforementioned specific compound containing carboxylic acid group, sulfonic group or phosphate or a variety of polymerizeing
It arrives, which is scattered in solvent with the second conducting polymer selected from polythiophene, polypyrrole, polyaniline simultaneously
In, the first conducting polymer and the second conducting polymer are combined by chemical bond form, the two not only compatibility and good dispersion,
And it can effectively improve charge in interfacial migration efficiency, to improve conductivity；Importantly, due to which it is conductive high to prepare first
Contain carboxylic acid group, sulfonic group or phosphate, the first conducting polymer and the second conducting polymer phase mutual connection in the compound of molecule
After touch, it is respectively played in polymeric dispersions by chemical bonds between the functional group of main function, it is stronger, it is poly- by this
Cycle charge discharge electrical property can be effectively improved by closing after object dispersion prepares solid electrolytic capacitor, will not be because of there is dedoping phenomenon
And the capacity extraction rate of solid electrolytic capacitor is caused to decline rapidly and the problem of ESR value increases rapidly.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
Polymeric dispersions provided by the invention include solvent and the first conducting polymer being scattered in solvent and
Two conducting polymers；
First conducting polymer is by selected from having one of following general formula compound represented or a variety of polymerize
It arrives:
Wherein, R indicates H or the linear chain or branched chain C1-C18 alkyl optionally replaced, the C5-C12 naphthenic base optionally replaced, appoints
The C6-C14 aryl for choosing generation, the C7-C18 aralkyl optionally replaced, in the C1-C4 hydroxy alkyl or hydroxyl that optionally replace extremely
Few one kind；
A indicates one of carboxylic acid group, sulfonic group or phosphate；
Y indicates one of NH, S；
N is the integer of 1-8；
X is selected from CO2、SO3One of；
Z is hydrogen or Na；
Second conducting polymer is selected from one of polythiophene, polypyrrole, polyaniline or a variety of.
It is chemical art according to known normal by the method that above compound polymerize the first conducting polymer of preparation
Know and to be easy to know.In the present invention, under preferable case, the preparation method of first conducting polymer can be with are as follows: in indifferent gas
It under atmosphere, contacts monomer with oxidant, is reacted, obtain the first conducting polymer.
Monomer in above-mentioned steps is selected from one of compound with following general formula or a variety of:
Wherein, R indicates H or the linear chain or branched chain C1-C18 alkyl optionally replaced, the C5-C12 naphthenic base optionally replaced, appoints
The C6-C14 aryl for choosing generation, the C7-C18 aralkyl optionally replaced, in the C1-C4 hydroxy alkyl or hydroxyl that optionally replace extremely
Few one kind；
A indicates one of carboxylic acid group, sulfonic group or phosphate；
Y indicates one of NH, S；
N is the integer of 1-8；
X is selected from CO2、SO3One of；
Z is hydrogen or Na.
Specifically, the monomer in the step can be first dissolved in solvent, monomer solution is obtained, convenient for operation and to reaction
The control of process.As known to a person skilled in the art, in the present invention, used solvent all can be in each step
Water.
Monomer employed in the present invention is as previously mentioned, be at least the aniline list containing carboxylic acid group, sulfonic group or phosphate
Body contains CO2、SO3Thiophene monomer.Those skilled in the art can as needed select the specific type of monomer.
As previously mentioned, under an inert atmosphere, contacting monomer with oxidant, reacted, obtains the first conducting polymer.
Inert atmosphere is atmosphere well known to chemical reaction field, such as can use nitrogen atmosphere.
Monomer can be carried out with reacting for oxidant in solvent environment, for example, can by monomer solution above-mentioned with contain
The oxidizing agent solution (solvent can be water) of oxidant is mixed, and reacts monomer with oxidant.
In the present invention, the oxidant is selected from potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, ferric sulfate, hydrogen peroxide, height
One of potassium manganate is a variety of.
The molar ratio of the monomer and oxidant determines, the two phase according to specific used monomer and oxidant species
It is that those skilled in the art are confirmable according to common knowledge to content.In the present invention, under preferable case, monomer and oxidant
Molar ratio be1:0.1-1:5。
Above-mentioned reaction can carry out at normal temperature, such as reaction temperature is 10-40 DEG C.
It can react to obtain first conducting polymer with specific structure through the above steps.According to the present invention, it also needs
Solution containing first conducting polymer is mixed with the solution containing the second conducting polymer, makes the first conducting polymer
It is reacted with the second conducting polymer, to obtain polymeric dispersions of the present invention.
Second conducting polymer is selected from one of polythiophene, polypyrrole, polyaniline or a variety of.
Further, the relative amount between the first conducting polymer and the second conducting polymer can be in a big way
It changes, under preferable case, the molar ratio of the first conducting polymer and the second conducting polymer is 1:0.5-1:4.
Further, the solvent is selected from one of water, ethyl alcohol or a variety of.
Under preferable case, the average grain diameter of first conducting polymer is 30- in polymeric dispersions provided by the invention
100nm.The average grain diameter of the second conducting polymer is 20-80nm in the polymeric dispersions.
Meanwhile the present invention also provides a kind of solid electrolytic capacitor, including core packet, the core packet includes successively being spaced to set
Anode, the first diaphragm, cathode, the second diaphragm set；The anode surface is attached with dielectric layer, and the dielectric layer surface is attached
Have a conductive polymer coating, the first conducting polymer and the second conducting polymer are contained in the conductive polymer coating；
First conducting polymer is by selected from having one of following general formula compound represented or a variety of polymerize
It arrives:
Wherein, R indicates H or the linear chain or branched chain C1-C18 alkyl optionally replaced, the C5-C12 naphthenic base optionally replaced, appoints
The C6-C14 aryl for choosing generation, the C7-C18 aralkyl optionally replaced, in the C1-C4 hydroxy alkyl or hydroxyl that optionally replace extremely
Few one kind；
A indicates one of carboxylic acid group, sulfonic group or phosphate；
Y indicates one of NH, S；
N is the integer of 1-8；
X is selected from CO2、SO3One of；
Z is hydrogen or Na；
Second conducting polymer is selected from one of polythiophene, polypyrrole, polyaniline or a variety of.
In above-mentioned solid electrolytic capacitor, the thickness of conductive polymer coating is preferably 120-160 μm.
Under preferable case, the average grain diameter of the first conducting polymer is 30-100nm in the conductive polymer coating.Second
The average grain diameter of conducting polymer is 20-80nm.
It is furthermore preferred that the molar ratio of the first conducting polymer and the second conducting polymer is 1 in the conductive polymer coating:
0.5-1:3。
Polymeric dispersions provided by the invention are suitable for all kinds of solid electrolytic capacitors, such as solid-state alminium electrolytic condenser
Device, solid-state tantalum electrolytic capacitor etc..
The present invention is further detailed by the following examples.
Embodiment 1
The present embodiment is used to illustrate the preparation method of polymeric dispersions disclosed by the invention, and uses the dispersion system
Standby solid electrolytic capacitor.
Each recipe ingredient of this example is separately added by following deal: pure water 150g, p-aminobenzene sulfonic acid 2.56g, is used
2.04g hydrogen peroxide makees oxidant, and reaction temperature is 20 DEG C, reaction time 20h, product (average grain diameter 40nm) and polythiophene
The molar ratio of homogenization after (average grain diameter 30nm) aqueous dispersion blending reaction, product and polypyrrole is 1:2.
Then it will be immersed in 30min and drying in the polymeric dispersions under solid electrolytic capacitor core packet condition of negative pressure,
It repeats the above steps 3 times, is assembled into solid electrolytic capacitor using sealing, conductive polymer coating is with a thickness of 130 μm.
The static capacity of capacitor, loss value and equivalent series resistance are surveyed using autoelectrinic part analysis instrument
Examination, test mode do not tire out state herein with reference to the measurement of conventional solid electrolytic capacitor.
Then it under the conditions of 1.15 times of voltage ratings, discharges within 3 seconds after carrying out charging in 3 seconds to solid electrolytic capacitor, repeatedly
Circulation 1000 times, again tests the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance.
Test result is as shown in table 1.
Embodiment 2
The present embodiment is used to illustrate the preparation method of polymeric dispersions disclosed by the invention, and uses the dispersion system
Standby solid electrolytic capacitor.
The technique and measurement method of this example are substantially the same manner as Example 1, and difference is: pure water 160g, orthanilic acid
2.73g makees oxidant using 2.53g potassium peroxydisulfate, and reaction temperature is 25 DEG C, reaction time 23h, and (average grain diameter is product
30nm) with polythiophene (average grain diameter 60nm) aqueous dispersion blending reaction after homogenization, product and polythiophene aqueous dispersion
Molar ratio be 1:1.
Then it will be immersed in 30min and drying in the polymeric dispersions under solid electrolytic capacitor core packet condition of negative pressure,
It repeats the above steps 3 times, is assembled into solid electrolytic capacitor using sealing, conductive polymer coating is with a thickness of 140 μm.
The static capacity of capacitor, loss value and equivalent series resistance are surveyed using autoelectrinic part analysis instrument
Examination, test mode do not tire out state herein with reference to the measurement of conventional solid electrolytic capacitor.
Then it under the conditions of 1.15 times of voltage ratings, discharges within 3 seconds after carrying out charging in 3 seconds to solid electrolytic capacitor, repeatedly
Circulation 1000 times, again tests the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance.
Test result is as shown in table 1.
Embodiment 3
The present embodiment is used to illustrate the preparation method of polymeric dispersions disclosed by the invention, and uses the dispersion system
Standby solid electrolytic capacitor.
The technique and measurement method of this example are substantially the same manner as Example 1, and difference is: pure water 168g, metanilic acid
Sodium 2.41g makees oxidant using 2.33g sodium peroxydisulfate, and reaction temperature is 18 DEG C, reaction time 26h, and (average grain diameter is product
60nm) with polyaniline (average grain diameter 40nm) aqueous dispersion blending reaction after homogenization, product and polyaniline aqueous dispersion
Molar ratio be 1:3.
Then it will be immersed in 30min and drying in the polymeric dispersions under solid electrolytic capacitor core packet condition of negative pressure,
It repeats the above steps 3 times, is assembled into solid electrolytic capacitor using sealing, conductive polymer coating is with a thickness of 120 μm.
The static capacity of capacitor, loss value and equivalent series resistance are surveyed using autoelectrinic part analysis instrument
Examination, test mode do not tire out state herein with reference to the measurement of conventional solid electrolytic capacitor.
Then it under the conditions of 1.15 times of voltage ratings, discharges within 3 seconds after carrying out charging in 3 seconds to solid electrolytic capacitor, repeatedly
Circulation 1000 times, again tests the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance.
Test result is as shown in table 1.
Embodiment 4
The present embodiment is used to illustrate the preparation method of polymeric dispersions disclosed by the invention, and uses the dispersion system
Standby solid electrolytic capacitor.
The technique and measurement method of this example are substantially the same manner as Example 1, and difference is: pure water 180g, 3- amino -4- methoxy
Base benzene sulfonic acid 3.61g makees oxidant using 2.51g ammonium persulfate, and reaction temperature is 26 DEG C, reaction time 21h, and product is (average
Partial size is 30nm) reacted with polypyrrole (average grain diameter 80nm) admixture of powder after homogenization, product and polypyrrole powder
Molar ratio is 1:0.5.
Then it will be immersed in 30min and drying in the polymeric dispersions under solid electrolytic capacitor core packet condition of negative pressure,
It repeats the above steps 3 times, is assembled into solid electrolytic capacitor using sealing, conductive polymer coating is with a thickness of 160 μm.
The static capacity of capacitor, loss value and equivalent series resistance are surveyed using autoelectrinic part analysis instrument
Examination, test mode do not tire out state herein with reference to the measurement of conventional solid electrolytic capacitor.
Then it under the conditions of 1.15 times of voltage ratings, discharges within 3 seconds after carrying out charging in 3 seconds to solid electrolytic capacitor, repeatedly
Circulation 1000 times, again tests the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance.
Test result is as shown in table 1.
Embodiment 5
The present embodiment is used to illustrate the preparation method of polymeric dispersions disclosed by the invention, and uses the dispersion system
Standby solid electrolytic capacitor.
The technique and measurement method of this example are substantially the same manner as Example 1, and difference is: pure water 143g, metanilic acid
Sodium 1.63g makees oxidant using 5.04g ferric sulfate, and reaction temperature is 15 DEG C, reaction time 10h, and (average grain diameter is product
80nm) with polythiophene (average grain diameter 50nem) aqueous dispersion blending reaction after homogenization, product and polythiophene aqueous dispersion
Molar ratio be 1:4.
Then it will be immersed in 30min and drying in the polymeric dispersions under solid electrolytic capacitor core packet condition of negative pressure,
It repeats the above steps 3 times, is assembled into solid electrolytic capacitor using sealing, conductive polymer coating is with a thickness of 140 μm.
The static capacity of capacitor, loss value and equivalent series resistance are surveyed using autoelectrinic part analysis instrument
Examination, test mode do not tire out state herein with reference to the measurement of conventional solid electrolytic capacitor.
Then it under the conditions of 1.15 times of voltage ratings, discharges within 3 seconds after carrying out charging in 3 seconds to solid electrolytic capacitor, repeatedly
Circulation 1000 times, again tests the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance.
Test result is as shown in table 1.
Embodiment 6
The present embodiment is used to illustrate the preparation method of polymeric dispersions disclosed by the invention, and uses the dispersion system
Standby solid electrolytic capacitor.
The technique and measurement method of this example are substantially the same manner as Example 1, and difference is: pure water 170g, 2- amino -5- methoxy
Base benzene sulfonic acid sodium salt 2.32g makees oxidant using 1.51g potassium permanganate, and reaction temperature is 35 DEG C, reaction time 30h, and product is (flat
Equal partial size is 100nm) and homogenization, product and polyaniline after polyaniline (average grain diameter 20nm) aqueous dispersion blending reaction
The molar ratio of aqueous dispersion is 1:1.
Then it will be immersed in 30min and drying in the polymeric dispersions under solid electrolytic capacitor core packet condition of negative pressure,
It repeats the above steps 3 times, is assembled into solid electrolytic capacitor using sealing, conductive polymer coating is with a thickness of 150 μm.
The static capacity of capacitor, loss value and equivalent series resistance are surveyed using autoelectrinic part analysis instrument
Examination, test mode do not tire out state herein with reference to the measurement of conventional solid electrolytic capacitor.
Then it under the conditions of 1.15 times of voltage ratings, discharges within 3 seconds after carrying out charging in 3 seconds to solid electrolytic capacitor, repeatedly
Circulation 1000 times, again tests the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance.
Test result is as shown in table 1.
Embodiment 7
The present embodiment is used to illustrate the preparation method of polymeric dispersions disclosed by the invention, and uses the dispersion system
Standby solid electrolytic capacitor.
The technique and measurement method of this example are substantially the same manner as Example 1, and difference is: pure water 190g, orthanilic acid
2.63g makees oxidant using 4.12g ammonium persulfate, and reaction temperature is 10 DEG C, and the reaction time, (average grain diameter was product for 24 hours
50nm) with polythiophene (average grain diameter 30nm) aqueous dispersion blending reaction after homogenization, product and polythiophene aqueous dispersion
Molar ratio be 1:3.
Then it will be immersed in 30min and drying in the polymeric dispersions under solid electrolytic capacitor core packet condition of negative pressure,
It repeats the above steps 3 times, is assembled into solid electrolytic capacitor using sealing, conductive polymer coating is with a thickness of 130 μm.
The static capacity of capacitor, loss value and equivalent series resistance are surveyed using autoelectrinic part analysis instrument
Examination, test mode do not tire out state herein with reference to the measurement of conventional solid electrolytic capacitor.
Then it under the conditions of 1.15 times of voltage ratings, discharges within 3 seconds after carrying out charging in 3 seconds to solid electrolytic capacitor, repeatedly
Circulation 1000 times, again tests the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance.
Test result is as shown in table 1.
Embodiment 8
The present embodiment is used to illustrate the preparation method of polymeric dispersions disclosed by the invention, and uses the dispersion system
Standby solid electrolytic capacitor.
The technique and measurement method of this example are substantially the same manner as Example 1, and difference is: pure water 180g, p-aminobenzene sulfonic acid
3.15g makees oxidant using 2.57g sodium peroxydisulfate, and reaction temperature is 40 DEG C, reaction time 20h, and (average grain diameter is product
40nm) with polyaniline (average grain diameter 50nm) aqueous dispersion blending reaction after homogenization, product and polyaniline aqueous dispersion
Molar ratio be 1:4.
Then it will be immersed in 30min and drying in the polymeric dispersions under solid electrolytic capacitor core packet condition of negative pressure,
It repeats the above steps 3 times, is assembled into solid electrolytic capacitor using sealing, conductive polymer coating is with a thickness of 120 μm.
The static capacity of capacitor, loss value and equivalent series resistance are surveyed using autoelectrinic part analysis instrument
Examination, test mode do not tire out state herein with reference to the measurement of conventional solid electrolytic capacitor.
Then it under the conditions of 1.15 times of voltage ratings, discharges within 3 seconds after carrying out charging in 3 seconds to solid electrolytic capacitor, repeatedly
Circulation 1000 times, again tests the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance.
Test result is as shown in table 1.
Comparative example 1
This comparative example is used for the preparation method of comparative illustration polymeric dispersions disclosed by the invention, and uses the dispersion
The solid electrolytic capacitor of body preparation.
Solid electrolytic capacitor core packet is impregnated with to conventional PEDOT/PSS aqueous dispersion under vacuum conditions, is impregnated with the time
For 30min, after toast 30min in 125 DEG C of baking ovens, repeat the above steps 3 times.Solid state electrolysis electricity is obtained by sealing assembly afterwards
Container.
Using autoelectrinic part analysis instrument to the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance
It is tested.Then it under the conditions of 1.15 times of voltage ratings, discharges within 3 seconds after carrying out charging in 3 seconds to solid electrolytic capacitor, repeatedly
Circulation 1000 times, again tests the static capacity of solid electrolytic capacitor, loss value and equivalent series resistance.
Test result is as follows for above embodiments and comparative example shown in table 1:
1 solid aluminum electrolytic capacitor properties test result of table (16V1000 μ F core packet)
It can be seen that the solid state electrolysis that the polymeric dispersions provided through the invention are prepared according to data in table 1
Capacitor after cycle charge-discharge capacity attenuation rate it is lower, attenuation rate is maximum to be also only -2.5%；And in comparative example
The solid electrolytic capacitor being prepared using conventional PEDOT/PSS aqueous dispersion is in the capacity attenuation after cycle charge-discharge
Rate is larger, is -21.0%, illustrates that polymeric dispersions of the invention are being not in dedoping after repeated charge substantially
The phenomenon that, the stability of polymeric dispersions is splendid, ensures that the stability of solid electrolytic capacitor performance, greatly mentions
The service life of solid electrolytic capacitor is risen.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of polymeric dispersions, which is characterized in that including solvent and the first conducting polymer being scattered in solvent and
Second conducting polymer；
First conducting polymer by being selected from there is one of following general formula compound represented or a variety of polymerizations to obtain:
Wherein, R indicates H or the linear chain or branched chain C1-C18 alkyl optionally replaced, the C5-C12 naphthenic base optionally replaced, optionally takes
The C6-C14 aryl in generation, the C7-C18 aralkyl optionally replaced, at least one in the C1-C4 hydroxy alkyl or hydroxyl that optionally replace
Kind；
A indicates one of carboxylic acid group, sulfonic group or phosphate；
Y indicates one of NH, S；
N is the integer of 1-8；
X is selected from CO2、SO3One of；
Z is hydrogen or Na；
Second conducting polymer is selected from one of polythiophene, polypyrrole, polyaniline or a variety of.
2. polymeric dispersions according to claim 1, which is characterized in that first conducting polymer and the second conduction
High molecular molar ratio is 1:0.5-1:6.
3. polymeric dispersions according to claim 1, which is characterized in that the solvent is selected from one of water, ethyl alcohol
Or it is a variety of.
4. polymeric dispersions according to claim 1, which is characterized in that first is conductive high in the polymeric dispersions
The average grain diameter of molecule is 20-150nm.
5. polymeric dispersions according to claim 1, which is characterized in that second is conductive high in the polymeric dispersions
The average grain diameter of molecule is 10-100nm.
6. a kind of solid electrolytic capacitor, which is characterized in that including core packet, the core packet include successively spaced anode,
First diaphragm, cathode, the second diaphragm；
The anode surface is attached with dielectric layer, and the dielectric layer surface is attached with conductive polymer coating, described conductive poly-
It closes and contains the first conducting polymer and the second conducting polymer in nitride layer；
First conducting polymer by being selected from there is one of following general formula compound represented or a variety of polymerizations to obtain:
Wherein, R indicates H or the linear chain or branched chain C1-C18 alkyl optionally replaced, the C5-C12 naphthenic base optionally replaced, optionally takes
The C6-C14 aryl in generation, the C7-C18 aralkyl optionally replaced, at least one in the C1-C4 hydroxy alkyl or hydroxyl that optionally replace
Kind；
A indicates one of carboxylic acid group, sulfonic group or phosphate；
Y indicates one of NH, S；
N is the integer of 1-8；
X is selected from CO2、SO3One of；
Z is hydrogen or Na；
Second conducting polymer is selected from one of polythiophene, polypyrrole, polyaniline or a variety of.
7. solid electrolytic capacitor according to claim 6, which is characterized in that the conductive polymer coating with a thickness of
100-200μm。
8. solid electrolytic capacitor according to claim 6 or 7, which is characterized in that first in the conductive polymer coating
The average grain diameter of conducting polymer is 20-150nm, and the average grain diameter of the second conducting polymer is in the conductive polymer coating
10-100nm。
9. solid electrolytic capacitor according to claim 6, which is characterized in that first is conductive in the conductive polymer coating
The molar ratio of macromolecule and the second conducting polymer is 1:0.5-1:6.
10. solid electrolytic capacitor according to claim 6, which is characterized in that the solid electrolytic capacitor is solid-state
Aluminium electrolutic capacitor or solid-state tantalum electrolytic capacitor.
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| WO2020063794A1 (en) * | 2018-09-29 | 2020-04-02 | 深圳新宙邦科技股份有限公司 | Polymer dispersion and preparation method therefor, and solid electrolytic capacitor |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000091081A (en) * | 1998-09-12 | 2000-03-31 | Bayer Ag | Auxiliary layer for electroluminescence assembly |
| JP2000208369A (en) * | 1999-01-13 | 2000-07-28 | Hitachi Chem Co Ltd | Solid electrolytic capacitor and manufacture thereof |
| CN1666302A (en) * | 2001-02-09 | 2005-09-07 | 纳幕尔杜邦公司 | Aqueous conductive dispersions of polyaniline having enhanced viscosity |
| CN1688633A (en) * | 2002-09-24 | 2005-10-26 | E.I.内穆尔杜邦公司 | Water dispersible polythiophenes made with polymeric acid colloids |
| CN101583671A (en) * | 2007-01-17 | 2009-11-18 | 荒川化学工业株式会社 | Organic solvent dispersion of conductive polymer/dopant and composition containing the dispersion |
| CN102245688A (en) * | 2008-10-20 | 2011-11-16 | 3M创新有限公司 | Electrically conductive composite material and thermoelectric device using electrically conductive polymer material |
| CN102558771A (en) * | 2010-12-30 | 2012-07-11 | 天津都创科技有限公司 | Poly 3,4-ethylenedioxy thiophene composite and preparation method thereof |
| CN103160122A (en) * | 2011-12-12 | 2013-06-19 | Nec东金株式会社 | Electroconductive polymer composition, electroconductive polymer material, electroconductive substrate, electrode and solid electrolytic capacitor |
| CN103562260A (en) * | 2011-05-30 | 2014-02-05 | Nec东金株式会社 | Conductive polymer, conductive polymer aqueous solution, conductive polymer film, solid electrolytic capacitor and method for producing same |
| CN105524463A (en) * | 2011-01-27 | 2016-04-27 | 出光兴产株式会社 | Polyaniline composite, method for producing same, and composition |
| CN106947221A (en) * | 2015-09-25 | 2017-07-14 | 信越化学工业株式会社 | Conductive polymer composition, cladding product and pattern formation method |
-
2018
- 2018-09-29 CN CN201811151153.0A patent/CN110010353B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000091081A (en) * | 1998-09-12 | 2000-03-31 | Bayer Ag | Auxiliary layer for electroluminescence assembly |
| JP2000208369A (en) * | 1999-01-13 | 2000-07-28 | Hitachi Chem Co Ltd | Solid electrolytic capacitor and manufacture thereof |
| CN1666302A (en) * | 2001-02-09 | 2005-09-07 | 纳幕尔杜邦公司 | Aqueous conductive dispersions of polyaniline having enhanced viscosity |
| CN1688633A (en) * | 2002-09-24 | 2005-10-26 | E.I.内穆尔杜邦公司 | Water dispersible polythiophenes made with polymeric acid colloids |
| CN101583671A (en) * | 2007-01-17 | 2009-11-18 | 荒川化学工业株式会社 | Organic solvent dispersion of conductive polymer/dopant and composition containing the dispersion |
| CN102245688A (en) * | 2008-10-20 | 2011-11-16 | 3M创新有限公司 | Electrically conductive composite material and thermoelectric device using electrically conductive polymer material |
| CN102558771A (en) * | 2010-12-30 | 2012-07-11 | 天津都创科技有限公司 | Poly 3,4-ethylenedioxy thiophene composite and preparation method thereof |
| CN105524463A (en) * | 2011-01-27 | 2016-04-27 | 出光兴产株式会社 | Polyaniline composite, method for producing same, and composition |
| CN103562260A (en) * | 2011-05-30 | 2014-02-05 | Nec东金株式会社 | Conductive polymer, conductive polymer aqueous solution, conductive polymer film, solid electrolytic capacitor and method for producing same |
| CN103160122A (en) * | 2011-12-12 | 2013-06-19 | Nec东金株式会社 | Electroconductive polymer composition, electroconductive polymer material, electroconductive substrate, electrode and solid electrolytic capacitor |
| CN106947221A (en) * | 2015-09-25 | 2017-07-14 | 信越化学工业株式会社 | Conductive polymer composition, cladding product and pattern formation method |
Non-Patent Citations (2)
| Title |
|---|
| KOBRYN, ALEXANDER E.; GUSAROV, SERGEY; SHANKAR, KARTHIK: ""The Effect of Molecular Structure and Environment on the Miscibility and Diffusivity in Polythiophene-Methanofullerene Bulk Heterojunctions: Theory and Modeling with the RISM Approach"", 《POLYMERS》 * |
| 李英梅: ""聚苯胺纳米结构的可控合成及性质研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020063794A1 (en) * | 2018-09-29 | 2020-04-02 | 深圳新宙邦科技股份有限公司 | Polymer dispersion and preparation method therefor, and solid electrolytic capacitor |
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