CN106893084B - A kind of dispersing agent makees the method that template in-situ polymerization prepares conducting polymer - Google Patents

A kind of dispersing agent makees the method that template in-situ polymerization prepares conducting polymer Download PDF

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CN106893084B
CN106893084B CN201710123195.2A CN201710123195A CN106893084B CN 106893084 B CN106893084 B CN 106893084B CN 201710123195 A CN201710123195 A CN 201710123195A CN 106893084 B CN106893084 B CN 106893084B
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thiophene
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谈利承
周环宇
陈义旺
周魏华
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Nanchang University
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Abstract

A kind of dispersing agent makees the method that template in-situ polymerization prepares conducting polymer, by in aqueous phase system, prepare the silver nanowires double-template aqueous dispersions of π dispersing agent template solution, the carbon material double-template aqueous dispersions of π dispersing agent dispersion and the modification of π dispersing agent, it is added [3,4- dioxoethyl] thiophene monomer and oxidizing agent solution, it is obtained by in-situ chemical polymerization.Method of the invention is simple, easy, controllable, and specific surface area with higher again while resulting composite material has a high conductivity therefore has a good application prospect in ultracapacitor energy storage device or area of solar cell.

Description

A kind of dispersing agent makees the method that template in-situ polymerization prepares conducting polymer
Technical field
The invention belongs to technical field of polymer composite materials, are related to the preparation method of conducting polymer.
Background technique
High conductivity and high transparency are the basic demands as transparent conductive film, in solar battery, display, gas Have in the devices such as quick element, transistor and widely applies.Tin indium oxide (ITO) has high transmitance and low square electricity Resistance, is widely applied transparent electrode material.But the major defect of ITO is that flexibility is poor, can reduce electric conductivity in turn not Conducive to device performance.In addition phosphide element is rare causes at high price, and to prepare ito thin film at high cost for magnetron sputtering method.Thus Need to find the transparent conductive film of suitable flexible printing to substitute ITO.
Conducting polymer is partly led due to having both the characteristics such as polymer architecture is various, easy to process, cheap and having Body, electrical property of metal etc., are expected to be used for the devices such as energy storage device, luminescent device, senser element, electrochromism, thus cause The extensive concern of domestic and international scientist.Poly- [3,4- ethene dioxythiophene]: polystyrolsulfon acid (PEDOT:PSS) is a kind of normal Conducting high polymers object, the preparation of film commercialization large-scale production simple compared to ITO, at low cost, suitable.It is by For polystyrolsulfon acid (PSS) as made of template in aqueous solution in-situ polymerization PEDOT, it includes the poly- of two kinds of opposite charges Close object PEDOT and PSS.Wherein, electronegative sulfonate radical has neutralized the PEDOT of positive charge doping, and remaining sulfonic group in PSS Group helps it to form dispersibility, the preferable PEDOT:PSS aqueous solution of translucency.But because the PSS of insulation exists, electric conductivity can't It meets the requirements, needs to further improve.
The method of modifying that research improves PEDOT:PSS transparent electrode electric conductivity mainly has: the doping of solvent and surface modification, Organic acid (formic acid) or inorganic acid (dense sulphur containing amphiphilic surfactant or zwitterionic classes compound, high dielectric constant Acid, hydrochloric acid, nitric acid etc.) it handles, carbon material (carbon nanotube and graphene) and metal nanometer line and PEDOT:PSS carry out compound. But which kind of either above method is modified PEDOT:PSS, and insulation, acid and hygroscopic PSS can influence material The electric conductivity of material and the stability of device.
High stability, agent of low hygroscopicity and the high conductivity that PEDOT is realized in order to avoid the PSS of addition insulation, can make It polymerize pure PEDOT with the method for polymerisation in solution or electrochemical polymerization, although theoretical electric conductivity is preferable, its insoluble insoluble property Matter limits its business application.So researcher attempts to be realized highly conductive with some novel templates come in-situ polymerization PEDOT The double dominant of property and polymolecularity.Yip et al. (Adv.Energy Mater., 2016,1601499) is with methyl naphthalene sulfonic acid salt Formaldehyde condensation products carry out in-situ polymerization PEDOT as template, and material applies the maximum electricity in blue phosphorescent Organic Light Emitting Diode Stream efficiency be 33.4cd/A, apply reached in perovskite battery 13.1% efficiency.Other than some organic polymers, Carbon material is also to select well as one for polymerizeing PEDOT template using its good thermoelectricity capability and conjugated structure.Hu etc. People (J.Mater.Chem.A, 2016,4,6645-6652) is acted synergistically using Sulfonated carbon nanotube as the second template and PSS In-situ polymerization PEDOT formed PEDOT:PSS:SCNT compound, electric conductivity is more than 3500S/cm, as electrode it is organic too Positive energy battery efficiency is 9.91%, and the efficiency of perovskite solar battery is 13.31%.Et al. (Carbon, 2017, 113,33-39) it uses the graphene of benzene sulfonate covalent functionalization as template in-situ polymerization PEDOT, is improved compared with original material Its electric conductivity and hole mobility.So the composite material based on PEDOT of in-situ polymerization has in contrast to PEDOT:PSS Very big advantage, needs to be studied and gathers around and have broad application prospects.Other than applying in transparent electrode, also potential application In antistatic, electric-control color-changeable glass, automobile electrically heated glass etc..
Summary of the invention
The object of the present invention is to provide a kind of dispersing agents to make the method that template in-situ polymerization prepares conducting polymer, in water phase In system, the carbon of small organic molecule or polymer, tetrasulfonic acid phenyl acid imide (PTS) dispersion with π structure containing sulfonic acid group Material, sulfydryl benzene sulfonic acid modification silver nanowires be template, in-situ chemical polymerization preparation excellent electrical property based on poly- [3,4- bis- Oxygen ethyl] thiophene (PEDOT) composite material method.
Poly- [3,4- dioxoethyl] thiophene (PEDOT) composite material of the invention is by being added π points in aqueous phase system Powder template, [3,4- dioxoethyl] thiophene (EDOT) monomer and oxidizing agent solution, are obtained by in-situ chemical polymerization, should Preparation method includes the following steps.
A) it takes water as a solvent, takes small organic molecule or polymer of a certain amount of π structure containing sulfonic acid group, ultrasound and hold Continuous stirring is dissolved, and obtaining mass fraction is the~π template dispersion liquid of 0.38wt%.
B) 0.5-2mg/mL carbon material is added in tetrasulfonic acid phenyl acid imide (PTS) solution, ultrasonic disperse stirring Until carbon material is dispersed in this system, carbon material double-template aqueous dispersions are obtained.
C) sulfydryl benzene sulfonic acid solution is added in 2-10mg/mL silver nanowires dispersion liquid, it is double stirs to get silver nanowires Template aqueous dispersions.
D) under agitation by [3,4- dioxoethyl] thiophene (EDOT) monomer be added separately to step a), step b), In the solution that step c) is obtained, three kinds of dispersion liquids are obtained；Wherein, the additional amount of EDOT are as follows: the matter of π template dispersing agent in step a) Amount is 0.26 with the mass ratio value that monomer EDOT is added；Tetrasulfonic acid phenyl acid imide (PTS) and carbon material are double in step b) The gross mass of template dispersing agent and the mass ratio value that monomer EDOT is added are 0.22-0.34；The silver nanoparticle modified in step c) The quality of line bimodulus version dispersing agent and the mass ratio value that monomer EDOT is added are 0.04-0.18.
E) oxidant for weighing certain mass is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57mol/L The aqueous solution of oxidant, in which: the volume ratio for the dispersion liquid that the aqueous solution and step d) of oxidant obtain is 1:4；Oxidant object The ratio of the amount of the substance of monomer EDOT is 1.2 in the amount and step d) dispersion liquid of matter.
F) under agitation, three kinds points for the obtained aqueous oxidizing agent solution of step e) being added separately to that step d) is obtained It in dispersion liquid, is stirred to react, is mixed thoroughly and reacts at room temperature, obtain (double) template in-situ polymerization PEDOT composite material Three kinds of black dispersion liquids；After the dialysis or dialysis and freeze-drying process to three kinds of black dispersion liquids, three kinds of final productions are obtained Object.
The π dispersing agent is the small organic molecule containing sulfonic acid group, including dodecyl benzene sulfonic acid (DBS), naphthalene sulfonic acids (NAS), tetrasulfonic acid phenyl acid imide (PTS) and the polymer containing sulfonic acid group include poly- [sulfonic acid butyl carbazole -1- thiophene] (PCART-SO3H) or poly- [1,4- bis- [sulfonic acid benzene butoxy] phenyl -1- thiophene] (Ph-1T)；Carbon material is graphene (Gra) Or multi-walled carbon nanotube (MWCNT).
The oxidant is ammonium persulfate (APS).
It is by matrix polymerization to the dialysis of three kinds of black dispersion liquids or dialysis and freeze-drying process described in step f) Three kinds of obtained black dispersion liquids are packed into bag filter, and dialyse 48h in deionized water, to silver nanowires bimodulus version aqueous dispersions It is directly saved after dialysis post-processing；To being freeze-dried for 24 hours after the dialysis of π template dispersion liquid and carbon material bimodulus version aqueous dispersions, Obtain three kinds of dispersion liquids or solid powder final product.
Method of the invention is simple, easy, controllable.The present invention mainly passes through polymerization [3,4- dioxy second in change system Base] thiophene (EDOT) template, obtain the compound based on poly- [3,4- dioxoethyl] thiophene (PEDOT) of different-shape and conductivity Material.Under conditions of no insulation PSS, the small organic molecule or polymerization of the electronegative different conjugated degrees containing sulfonic acid group There are electrostatic attractions and π-π to interact between object and positively charged PEDOT, is used as template in-situ polymerization PEDOT.In addition, Organic conjugate small molecule again can be as surfactant by π-π interaction dispersion carbon material, or passes through sulfydryl and metal Ligand complex effect dispersion silver nanowires, forms the aqueous dispersions of stable uniform so as to form double-template system in-situ polymerization PEDOT forms a kind of advanced composite material (ACM) of inierpeneirating network structure.The resulting composite material of the present invention is with high conductivity While and specific surface area with higher, therefore have in ultracapacitor energy storage device or area of solar cell and answer well Use prospect.
Detailed description of the invention
Fig. 1 is poly- [the 3,4- dioxy second by dodecyl benzene sulfonic acid (DBS) as matrix polymerization of the embodiment of the present invention 1 Base] thiophene (PEDOT) composite material transmission electron microscope photo.
Fig. 2 is poly- [3,4- dioxoethyl] thiophene by naphthalene sulfonic acids (NAS) as matrix polymerization of the embodiment of the present invention 2 (PEDOT) transmission electron microscope photo of composite material.
Fig. 3 is the poly- [3,4- bis- by tetrasulfonic acid phenyl acid imide (PTS) as matrix polymerization of the embodiment of the present invention 3 Oxygen ethyl] thiophene (PEDOT) composite material transmission electron microscope photo.
Fig. 4 is the embodiment of the present invention 4 by polymer poly [sulfonic acid butyl carbazole -1- thiophene] (PCART-SO3H) it is used as mould The transmission electron microscope photo of poly- [3,4- dioxoethyl] thiophene (PEDOT) composite material of plate polymerization.
Fig. 5 is the embodiment of the present invention 5 by polymer poly [1,4- bis- [sulfonic acid benzene butoxy] phenyl -1- thiophene] (Ph- 1T) the transmission electron microscope photo as poly- [3,4- dioxoethyl] thiophene (PEDOT) composite material of matrix polymerization.
Fig. 6 is the multi-walled carbon nanotube of the embodiment of the present invention 6 dispersed by tetrasulfonic acid phenyl acid imide (PTS) (MWCNT) transmission electron microscope photo as poly- [3,4- dioxoethyl] thiophene (PEDOT) composite material of double-template polymerization.
Fig. 7 is the graphene (Gra) by tetrasulfonic acid phenyl acid imide (PTS) dispersion of the embodiment of the present invention 7 as double The transmission electron microscope photo of poly- [3,4- dioxoethyl] thiophene (PEDOT) composite material of matrix polymerization.
Fig. 8 is for the embodiment of the present invention 4 with embodiment 5 by polymer poly [sulfonic acid butyl carbazole -1- thiophene] (PCART- SO3) and poly- [1,4- bis- [sulfonic acid benzene butoxy] phenyl -1- thiophene] poly- [the 3,4- dioxy second of (Ph-1T) as matrix polymerization H Base] thiophene (PEDOT) composite material light transmittance picture.
Specific embodiment
The present invention will be described further by following embodiment.
Embodiment 1.
A) take water as a solvent, take a certain amount of surfactant sodium dodecyl base benzene sulfonic acid (DBS) soluble in water, ultrasound and Lasting stirring is dissolved, and the clear solution that DBS concentration is 0.01mol/L is obtained.
B) under agitation, by monomer 3,4- ethylenedioxythiophene (EDOT) is added in the solution that step a) is obtained, Wherein: the amount of the substance of the EDOT of addition is 10 times (3.85 times of quality) of the amount of the substance of the DBS in step a)；In room temperature Lower stirring 2 hours, obtains evenly dispersed mixed liquor.
C) ammonium persulfate (APS) is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57mol/L over cure The transparent aqueous solution of sour ammonium；The ratio of the amount of the substance of monomer EDOT is in the amount and step b) dispersion liquid of ammonium persulfate substance 1.2。
D) transparent aqueous solution containing ammonium persulfate that step c) is obtained is added into step b) solution, is sufficiently stirred, directly To being mixed thoroughly；Reaction 48 hours is stirred at room temperature, obtains poly- [3, the 4- dioxoethyl] using DBS as the polymerization of template The black mixed liquor of thiophene (PEDOT) composite material；Wherein: transparent aqueous solution of the step c) containing ammonium persulfate and step b) points The volume ratio of dispersion liquid is 1:4.
E) through dialysis, filter and be dried to obtain the PEDOT composite materials of the microcosmic excellent electrical properties for isolated granule-morphology Powder, transmission electron microscope photo is referring to Fig. 1.
Embodiment 2.
A) take water as a solvent, take a certain amount of surfactant naphthalene sulfonic acids (NAS) soluble in water, ultrasound and continue to stir It is dissolved, obtains the clear solution that NAS concentration is 0.02mol/L.
B) under agitation, by monomer 3,4- ethylenedioxythiophene (EDOT) is added in the solution that step a) is obtained, Wherein: the amount of the substance of the EDOT of addition is 6.5 times (3.85 times of quality) of the amount of the substance of the NAS in step a)；In room Temperature lower stirring 2 hours, obtain evenly dispersed mixed liquor.
C) ammonium persulfate (APS) is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57mol/L over cure The transparent aqueous solution of sour ammonium；The ratio of the amount of the substance of monomer EDOT is in the amount and step b) dispersion liquid of ammonium persulfate substance 1.2。
D) transparent aqueous solution containing ammonium persulfate that step c) is obtained is added into step b) solution, is sufficiently stirred, directly To being mixed thoroughly；Reaction 48 hours is stirred at room temperature, obtains poly- [3, the 4- dioxoethyl] thiophene using NAS as template (PEDOT) the black mixed liquor of composite material；Wherein: transparent aqueous solution of the step c) containing ammonium persulfate and step b) dispersion liquid Volume ratio be 1:4.
E) through dialysis, filter and be dried to obtain the PEDOT composite wood feed powders of the microcosmic excellent electrical properties for strip pattern End, transmission electron microscope photo is referring to fig. 2.
Embodiment 3.
A) take water as a solvent, take a certain amount of tetrasulfonic acid phenyl acid imide (PTS) soluble in water, ultrasound and persistently stir It mixes and is dissolved, obtain the purple solution that PTS concentration is 0.003mol/L.
B) under agitation, by monomer 3,4- ethylenedioxythiophene (EDOT) is added in the solution that step a) is obtained, Wherein: the amount of the substance of the EDOT of addition is 42 times (3.85 times of quality) of the amount of the substance of the PTS in step a)；In room temperature Lower stirring 2 hours, obtains evenly dispersed mixed liquor.
C) ammonium persulfate (APS) is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57mol/L over cure The transparent aqueous solution of sour ammonium；The ratio of the amount of the substance of monomer EDOT is in the amount and step b) dispersion liquid of ammonium persulfate substance 1.2。
D) transparent aqueous solution containing ammonium persulfate that step c) is obtained is added into step b) solution, is sufficiently stirred, directly To being mixed thoroughly；Reaction 48 hours is stirred at room temperature, obtains poly- [3, the 4- dioxoethyl] thiophene using PTS as template (PEDOT) the black mixed liquor of composite material；Wherein: transparent aqueous solution of the step c) containing ammonium persulfate and step b) dispersion liquid Volume ratio be 1:4.
E) through dialysis, filter and be dried to obtain the PEDOT composite wood feed powders of the microcosmic excellent electrical properties for big sheet-like morphology End, transmission electron microscope photo is referring to Fig. 3.
Embodiment 4.
A) it takes water as a solvent, takes a certain amount of polymer poly [sulfonic acid butyl carbazole -1- thiophene] (PCART-SO3H it) is dissolved in In water, heats and continue stirring and dissolved, obtain polymer PC ART-SO3The mass concentration of H is the pale yellow of 3.75mg/mL Color solution；
B) under agitation, by monomer 3,4- ethylenedioxythiophene (EDOT) is added in the solution that step a) is obtained, The quality of the EDOT of addition is the PCART-SO in step a)33.85 times of H mass are stirred at room temperature 2 hours, obtain uniformly The mixed liquor of dispersion.
C) ammonium persulfate (APS) is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57mol/L over cure The transparent aqueous solution of sour ammonium；The ratio of the amount of the substance of monomer EDOT is in the amount and step b) dispersion liquid of ammonium persulfate substance 1.2。
D) transparent aqueous solution containing ammonium persulfate that step c) is obtained is added into step b) solution, is sufficiently stirred, directly To being mixed thoroughly；Reaction 48 hours is stirred at room temperature, obtains with polymer PC ART-SO3H is the poly- [3,4- bis- of template Oxygen ethyl] thiophene (PEDOT) composite material dark solution；Wherein: transparent aqueous solution and step of the step c) containing ammonium persulfate The volume ratio of rapid b) dispersion liquid is 1:4.
E) the PEDOT composite material solution of the microcosmic excellent electrical properties for strip pattern, transmission electron microscope are obtained through dialysis Photo is referring to fig. 4；Light transmittance picture is referring to Fig. 8.
Embodiment 5.
A) it takes water as a solvent, takes a certain amount of polymer poly [Isosorbide-5-Nitrae-two [sulfonic acid benzene butoxy] phenyl -1- thiophene] (Ph- It is 1T) soluble in water, ultrasound and continue stirring dissolved, obtain polymer P h-1T mass concentration be 3.75mg/mL it is red Brown solution.
B) under agitation, by monomer 3,4- ethylenedioxythiophene (EDOT) is added in the solution that step a) is obtained, The quality of the EDOT of addition is 3.85 times of the Ph-1T mass in step a), is stirred at room temperature 2 hours, obtains evenly dispersed Mixed liquor.
C) ammonium persulfate (APS) is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57mol/L over cure The transparent aqueous solution of sour ammonium；The ratio of the amount of the substance of monomer EDOT is in the amount and step b) dispersion liquid of ammonium persulfate substance 1.2。
D) transparent aqueous solution containing ammonium persulfate that step c) is obtained is added into step b) solution, is sufficiently stirred, directly To being mixed thoroughly；Reaction 48 hours is stirred at room temperature, obtains poly- [3, the 4- dioxy second using polymer P h-1T as template Base] thiophene (PEDOT) composite material dark solution；Wherein: transparent aqueous solution of the step c) containing ammonium persulfate and step b) The volume ratio of dispersion liquid is 1:4.
E) the PEDOT composite material solution of the microcosmic excellent electrical properties for uniform film morphology, transmission electricity are obtained through dialysis Mirror photo is referring to Fig. 5；Light transmittance picture is referring to Fig. 8.
Embodiment 6.
A) take water as a solvent, take a certain amount of tetrasulfonic acid phenyl acid imide (PTS) soluble in water, ultrasound and persistently stir It mixes and is dissolved, obtain the purple solution that PTS concentration is 0.0025mol/L.
B) 1mg/mL multi-walled carbon nanotube (MWCNT) is incorporated in the purple solution of step a), ultrasonic disperse, Zhi Daoduo Wall carbon nano tube is dispersed in this mixed system, obtains the multi-walled carbon nanotube dispersion liquid that mass fraction is 0.001%.
C) under agitation, by monomer 3,4- ethylenedioxythiophene (EDOT) is added to the multi wall carbon that step b) is obtained and receives In mitron dispersion liquid, in which: the amount of the substance of the EDOT of addition is 50 times of the amount of the substance of the PTS in step a)；It is added The quality of EDOT is 3.85 times of the quality of the double-template in step b)；It is stirred at room temperature 2 hours, obtains evenly dispersed mix Close liquid.
D) ammonium persulfate (APS) is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57mol/L over cure The transparent aqueous solution of sour ammonium；The ratio of the amount of the substance of monomer EDOT is in the amount and step c) dispersion liquid of ammonium persulfate substance 1.2。
E) transparent aqueous solution containing ammonium persulfate that step d) is obtained is added into step c) solution, is sufficiently stirred, directly To being mixed thoroughly；Reaction 48 hours is stirred at room temperature, obtains poly- [3, the 4- dioxy second using PTS:MWCNT as double-template Base] thiophene (PEDOT) composite material black mixed liquor；Wherein: transparent aqueous solution and step of the step d) containing ammonium persulfate B) volume ratio of dispersion liquid is 1:4.
F) through dialysis, filter and be dried to obtain it is microcosmic for by PEDOT coat multi-walled carbon nanotube interpenetrating network shape The PEDOT composite powder of the excellent electrical properties of looks, transmission electron microscope photo is referring to Fig. 6.
Embodiment 7.
A) take water as a solvent, take a certain amount of tetrasulfonic acid phenyl acid imide (PTS) soluble in water, ultrasound and persistently stir It mixes and is dissolved, obtain the purple solution that PTS concentration is 0.0025mol/L.
B) graphene of 1mg/mL (Gra) is incorporated in the purple solution of step a), ultrasonic disperse, until graphene is equal It is even to be scattered in this mixed system, obtain the graphene dispersing solution that mass fraction is 0.001%.
C) under agitation, by monomer 3,4- ethylenedioxythiophene (EDOT) is added to the graphene point that step b) is obtained In dispersion liquid, in which: the amount of the substance of the EDOT of addition is 50 times of the amount of the substance of the PTS in step a)；The EDOT's of addition Quality is 3.85 times of the quality of the double-template in step b)；It is stirred at room temperature 2 hours, obtains evenly dispersed mixed liquor.
D) ammonium persulfate (APS) is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57mol/L over cure The transparent aqueous solution of sour ammonium；The ratio of the amount of the substance of monomer EDOT is in the amount and step c) dispersion liquid of ammonium persulfate substance 1.2。
E) transparent aqueous solution containing ammonium persulfate that step d) is obtained is added into step c) solution, is sufficiently stirred, directly To being mixed thoroughly；Reaction 48 hours is stirred at room temperature, obtains poly- [3, the 4- dioxoethyl] using PTS:Gra as double-template The black mixed liquor of thiophene (PEDOT) composite material；Wherein: transparent aqueous solution of the step d) containing ammonium persulfate and step b) points The volume ratio of dispersion liquid is 1:4.
F) through dialysis, to filter and be dried to obtain microcosmic be the excellent electrical properties for being grown on graphene surface PEDOT structure PEDOT composite powder, transmission electron microscope photo is referring to Fig. 7.
Embodiment 8.
A) take water as a solvent, take a certain amount of pair of sulfydryl benzene sulfonic acid soluble in water, ultrasound and continue stirring dissolved, Obtain the clear solution for being 0.005mol/L to sulfydryl benzene sulfonic acid concentration.
B) sulfydryl benzene sulfonic acid solution is added in 5mg/mL silver nanowires dispersion liquid, stirs to get mercapto-modified content For 0.5% silver nanowires double-template aqueous dispersions.
C) under agitation, by monomer 3,4- ethylenedioxythiophene (EDOT) is added to the silver for the modification that step b) is obtained In nano wire double-template dispersion liquid, in which: the quality of the EDOT of addition is 11 times of the quality of the double-template in step b)；In room Temperature lower stirring 2 hours, obtain evenly dispersed mixed liquor.
D) ammonium persulfate (APS) is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57mol/L over cure The transparent aqueous solution of sour ammonium；The ratio of the amount of the substance of monomer EDOT is in the amount and step c) dispersion liquid of ammonium persulfate substance 1.2。
E) transparent aqueous solution containing ammonium persulfate that step d) is obtained is added into step c) solution, is sufficiently stirred, directly To being mixed thoroughly；Reaction 48 hours is stirred at room temperature, obtains poly- [3, the 4- dioxies with the silver nanowires double-template of modification Ethyl] thiophene (PEDOT) composite material black mixed liquor.
F) the PEDOT composite material dispersion for the excellent electrical properties polymerizeing with the silver nanowires double-template of modification is obtained through dialysing Liquid.

Claims (5)

1. a kind of dispersing agent makees the method that template in-situ polymerization prepares conducting polymer, it is characterized in that the following steps are included:
A) it takes water as a solvent, takes small organic molecule or polymer of a certain amount of π structure containing sulfonic acid group, it is ultrasonic and lasting Stirring is dissolved, and the π template dispersion liquid that mass fraction is 0.38 wt% is obtained；
B) 0.5-2 mg/mL carbon material is added in tetrasulfonic acid phenyl imide solution, ultrasonic disperse is stirred until carbon Material is dispersed in this system, obtains carbon material double-template aqueous dispersions；
C) sulfydryl benzene sulfonic acid solution is added in 2-10 mg/ mL silver nanowires dispersion liquid, it is double stirs to get silver nanowires Template aqueous dispersions；
D) under agitation by [3,4- dioxoethyl] thiophene be added separately to step a), step b), step c) obtain it is molten In liquid, three kinds of dispersion liquids are obtained；Wherein, the additional amount of [3,4- dioxoethyl] thiophene are as follows: π template dispersion liquid in step a) Solute mass and the mass ratio value that [3,4- dioxoethyl] thiophene is added are 0.26；Tetrasulfonic acid phenyl acyl is sub- in step b) The mass ratio value of the gross mass and addition [3,4- dioxoethyl] thiophene of amine and carbon material double-template dispersing agent is 0.22- 0.34；The quality of the silver nanowires double-template dispersing agent modified in step c) and the quality of addition [3,4- dioxoethyl] thiophene it Ratio is 0.04-0.18；
E) oxidant for weighing certain mass is dissolved in deionized water, stirring and dissolving, obtains containing concentration being 0.57 mol/L oxygen The aqueous solution of agent, in which: the volume ratio for the dispersion liquid that the aqueous solution and step d) of oxidant obtain is 1:4；Oxidant species Amount and step d) dispersion liquid in [3,4- dioxoethyl] thiophene substance amount ratio be 1.2；
F) under agitation, aqueous oxidizing agent solution step e) obtained is added separately to three kinds of dispersion liquids that step d) obtains In, it is stirred to react at room temperature, is mixed thoroughly and reacts, obtain poly- [3, the 4- dioxoethyl] thiophene of (double) template in-situ polymerization Three kinds of black dispersion liquids of pheno composite material；To the dialysis treatment of three kinds of black dispersion liquids, or dialysis and freeze-drying process, Obtain three kinds of final products.
2. a kind of dispersing agent according to claim 1 makees the method that template in-situ polymerization prepares conducting polymer, feature It is that the small organic molecule containing sulfonic acid group is dodecyl benzene sulfonic acid, naphthalene sulfonic acids, tetrasulfonic acid phenyl acid imide and contains The polymer of sulfonic acid group is poly- [sulfonic acid butyl carbazole -1- thiophene] or poly- [1,4- bis- [sulfonic acid benzene butoxy] phenyl -1- thiophene Pheno].
3. a kind of dispersing agent according to claim 1 makees the method that template in-situ polymerization prepares conducting polymer, feature Be the carbon material be graphene or multi-walled carbon nanotube.
4. a kind of dispersing agent according to claim 1 makees the method that template in-situ polymerization prepares conducting polymer, feature It is the oxidant is ammonium persulfate.
5. a kind of dispersing agent according to claim 1 makees the method that template in-situ polymerization prepares conducting polymer, feature It is described in step f) is that three kinds of black dispersion liquids obtaining matrix polymerization fill to the dialysis treatment of three kinds of black dispersion liquids Enter bag filter, dialyse 48h in deionized water；
Described is that three kinds of black for obtaining matrix polymerization disperse to the dialysis of three kinds of black dispersion liquids and freeze-drying process Liquid is packed into bag filter, is freeze-dried for 24 hours after the 48h that dialyses in deionized water.
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