WO2012088691A1 - 导电高分子材料及其制备方法和应用 - Google Patents

导电高分子材料及其制备方法和应用 Download PDF

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WO2012088691A1
WO2012088691A1 PCT/CN2010/080512 CN2010080512W WO2012088691A1 WO 2012088691 A1 WO2012088691 A1 WO 2012088691A1 CN 2010080512 W CN2010080512 W CN 2010080512W WO 2012088691 A1 WO2012088691 A1 WO 2012088691A1
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conductive polymer
polymer material
solution
fluorinated graphene
preparing
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PCT/CN2010/080512
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English (en)
French (fr)
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周明杰
钟玲珑
王要兵
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海洋王照明科技股份有限公司
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Priority to US13/988,114 priority Critical patent/US9142330B2/en
Priority to CN201080069880.8A priority patent/CN103181001B/zh
Priority to EP10861504.8A priority patent/EP2660900B1/en
Priority to PCT/CN2010/080512 priority patent/WO2012088691A1/zh
Priority to JP2013546554A priority patent/JP2014502653A/ja
Publication of WO2012088691A1 publication Critical patent/WO2012088691A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0464—Electro organic synthesis
    • H01M4/0466—Electrochemical polymerisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the technical field of polymer materials, and in particular relates to a conductive polymer material, a preparation method thereof and an application thereof.
  • the conductive polymer is a kind of high-molecular material which has a large conjugated ⁇ bond structure and has a conductivity of chemically or electrochemically doped to extend from the insulator to the conductor.
  • the conductive polymer material has the advantages of good electrical conductivity, simple preparation method and long storage time.
  • the existing conductive polymer material has poor cycle stability and is prone to instability during application.
  • the embodiments of the present invention provide a conductive polymer material, which solves the technical problem of poor cycle performance of the conductive polymer material in the prior art.
  • the embodiment of the invention further provides a method for preparing a conductive polymer material.
  • Embodiments of the present invention also provide the use of the above conductive polymer material in a solar cell, an organic electroluminescent device or a lithium ion battery.
  • the present invention is implemented in this way,
  • a conductive polymer material comprising a conductive polymer and fluorinated graphene doped in the conductive polymer, the conductive polymer and the fluorinated graphene having a mass ratio of 1:0.05-1, wherein the conductive polymer is Polythiophene or a derivative thereof, polypyrrole or a derivative thereof, and one of polyaniline or a derivative thereof.
  • the fluorinated graphene is dissolved in a surfactant-containing solution to obtain a first solution;
  • the organic monomer is added to the first solution according to the mass ratio of the organic monomer and the fluorinated graphene 1:0.05-1, the electrolyte is added, the working electrode and the counter electrode are placed, and electrochemical polymerization is performed by electricity to obtain a conductive polymer material.
  • the organic monomer is one of aniline or a derivative thereof, pyrrole or a derivative thereof, and thiophene or a derivative thereof.
  • Embodiments of the present invention also provide the use of the above conductive polymer material in a solar cell, an organic electroluminescent device or a lithium ion battery.
  • the cyclic stability of the conductive polymer material is greatly enhanced by doping the fluorinated graphene, and at the same time, the conductive polymer has excellent capacity performance.
  • the preparation method of the embodiment of the invention has the advantages of simple operation, low cost, low requirement on equipment, and is suitable for industrial production.
  • Fig. 1 is a graph showing the cycle life of a conductive polymer material in 1 mol/L of sulfuric acid according to an embodiment of the present invention.
  • a conductive polymer material comprising a conductive polymer and fluorinated graphene doped in the conductive polymer, the conductive polymer and the fluorinated graphene having a mass ratio of 1:0.05-1, wherein the conductive polymer is Polythiophene or a derivative thereof, polypyrrole or a derivative thereof, and one of polyaniline or a derivative thereof.
  • the conductive polymer material of the embodiment of the invention comprises fluorinated graphene, and polythiophene or a derivative thereof, polypyrrole or a derivative thereof, or one of polyaniline or a derivative thereof.
  • Fluorinated graphene has good cycle stability performance, can greatly increase the cycle stability performance of the conductive polymer material of the embodiment of the invention, and increases its service life; meanwhile, the above conductive polymer has excellent capacity properties, so that the embodiment of the invention is electrically conductive.
  • the polymer compound has a high capacity.
  • the fluorinated graphene has excellent electrical conductivity, and the conductive property of the conductive polymer material of the embodiment of the present invention is remarkably enhanced by doping the fluorinated graphene.
  • the mass ratio of the conductive polymer to the graphene fluoride is 1:0.05-1, preferably 1:0.5-1.
  • the fluorinated graphene is doped in the conductive polymer; in some embodiments, the long chain of the conductive polymer forms a network structure, and the fluorinated graphene is located in the network structure, that is, the conductive polymer The fluorinated graphene is surrounded.
  • the embodiment of the invention further provides a method for preparing a conductive polymer material, comprising the following steps:
  • the fluorinated graphene is dissolved in a surfactant-containing solution to obtain a first solution;
  • the organic monomer is added to the first solution at a mass ratio of organic monomer to fluorinated graphene of 1:0.05-1, an electrolyte is added, a working electrode and a counter electrode are placed, and electrochemical polymerization is carried out to obtain a conductive polymer material.
  • the surfactant is an anionic surfactant, a cationic surfactant or a nonionic surfactant or an amphoteric surfactant.
  • the anionic surfactant is selected from the group consisting of alkylbenzene sulfonate, fatty alcohol sulfate, phosphate, sodium dodecylbenzenesulfonate or sodium methylbenzenesulfonate;
  • the cationic surfactant is selected from the group consisting of fatty amines, amine oxidation a quaternary ammonium salt or tetraethylammonium chloride;
  • the nonionic surfactant is selected from the group consisting of fatty alcohol polyoxyethylene ethers, alkylphenol ethoxylates, carboxylates or fatty alcohol amides; From imidazoline.
  • the concentration of the surfactant in the surfactant-containing solution is from 0.01 to 0.6 mol/L, and the solvent used is water or another solvent.
  • the fluorinated graphene is dissolved in the surfactant-containing solution at a mass fraction of fluorinated graphene of 0.01 to 0.1%, and then ultrasonically shaken for 5 minutes to 2 hours to obtain a first solution.
  • the compatibility between the fluorinated graphene and the surfactant is such that a solution containing a surfactant is used as a solvent for the graphene fluoride to ensure complete dissolution and dispersion of the fluorinated graphene.
  • the fluorinated graphene used in the production method of the embodiment of the present invention is not limited, and may be a commercially available fluorinated graphene or a self-made fluorinated graphene.
  • a commercially available fluorinated graphene or a self-made fluorinated graphene.
  • self-made fluorinated graphene is used, and the preparation process is as follows:
  • graphene is added to the reactor, and a mixed gas composed of fluorine gas or fluorine gas and an inert gas is introduced, and the reaction is carried out at a temperature of 50-500 ° C for 3-120 h to obtain fluorinated graphene.
  • the inert gas means nitrogen gas, helium gas, argon gas, helium gas or the like.
  • the fluorine-nitrogen mixed gas is introduced into the reactor, and the fluorine gas accounts for 10-30% of the volume of the mixed gas, and nitrogen is used as a dilution gas of fluorine.
  • the fluorine gas is introduced into the total volume by 20%.
  • the fluorine-nitrogen mixed gas was reacted at 250 ° C for 6 h.
  • the anaerobic condition is not limited, and it is ensured that no oxygen is present during the entire reaction.
  • nitrogen, argon or helium is introduced into the reactor for 0.5-4 hours, and then sealed. Under the conditions, the above reaction gas is introduced; under anhydrous conditions, the graphene is dried before the reaction, and a dry fluorine gas or a mixed gas of fluorine gas and an inert gas is introduced.
  • the organic monomer means thiophene or a derivative thereof, aniline or a derivative thereof, pyrrole or a derivative thereof.
  • the organic monomer is added to the first solution to obtain a second solution.
  • the organic monomer concentration is 0.01-0.6 mol/L, and the mass ratio of the organic monomer to the fluorinated graphene is 1:0.01- 1.
  • the electrolyte is added to the second solution, which is not limited, can be dissolved in the above second solution and is electrically conductive, for example, potassium chloride, sodium chloride, potassium chlorate, potassium perchlorate, sodium bromide, potassium bromide, potassium iodide.
  • sodium iodide, potassium nitrate, sodium nitrate or sodium sulfate is a third solution is obtained, and the concentration of the electrolyte in the third solution is 0.001-0.3. Mol/L.
  • the working electrode and the counter electrode are placed in the third solution, and a current of a current density of 0.1-10 mA/cm 2 is applied to the working electrode for electrochemical polymerization, and the organic monomer is polymerized under the electric field to form a long chain.
  • a conductive polymer, a plurality of the long-chain conductive polymers aggregate to form a network structure or other structure, further, the network structure surrounds the fluorinated graphene, and the fluorinated graphene is uniformly doped between the conductive polymers at the working electrode
  • a uniform composite film, that is, a conductive polymer material, is formed thereon.
  • the thickness of the composite film of the polymer material can be controlled by controlling the amount of electric current flowing through the polymerization process.
  • the working electrode can be used as a base material of the supercapacitor electrode plate, and the working electrode formed with the conductive polymer material composite film can be directly used as the supercapacitor electrode.
  • the conductive polymer material is prepared by an electrochemical polymerization method, so that the conductive polymer and the fluorinated graphene are more uniformly doped in the polymer material, thereby greatly improving the conductive property and the cycle stability of the conductive polymer material. performance.
  • the cyclic stability of the conductive polymer material is greatly enhanced by doping the fluorinated graphene, and at the same time, the conductive polymer has excellent capacity performance.
  • the preparation method of the embodiment of the invention has the advantages of simple operation, low cost, low requirement on equipment, and is suitable for industrial production.
  • the embodiment of the invention further provides the application of the above conductive polymer material in a solar cell, an organic electroluminescent device, and a lithium ion battery.
  • the graphene was dried in a dry box for 24 hours, placed in a reactor, and passed through a dry nitrogen gas for 0.5 h, then passed through a fluorine gas, and reacted at 300 ° C for 12 h to obtain a graphene fluoride;
  • the fluorinated graphene is ultrasonically shaken in a solution of 0.5 mol/L of dodecylbenzenesulfonic acid for 30 minutes to obtain a first solution having a fluorinated graphene mass percentage of 0.035%;
  • the working electrode and the counter electrode were placed in a third solution, and a current density current of 10 mA/cm 2 was applied to the working electrode to carry out electrochemical polymerization to obtain a conductive polymer material.
  • FIG. 1 is a diagram showing the cycle life of an electrode made of the conductive polymer material prepared in Example 1 in 1 mol/L of sulfuric acid.
  • the test conditions are: current density is 0.2 A/g, and the cutoff voltage range is 0-1V, cycle 1000 times.
  • the initial capacity is 372F / g
  • the capacity still retains 350 after 1000 cycles F/g
  • the conductive polymer material of the embodiment of the invention has excellent cycle stability performance.
  • the graphene was dried in a dry box for 24 hours, and then placed in a reactor, and dried nitrogen gas was introduced for 0.5 h, and then a fluorine-nitrogen mixed gas containing 20% of the total volume of fluorine gas was introduced, and the reaction was carried out at 100 ° C for 75 hours.
  • the fluorinated graphene is ultrasonically oscillated in a solution of 0.01 mol/L of dodecylbenzenesulfonic acid for 5 min to obtain a first solution having a mass percentage of fluorinated graphene of 0.056%;
  • the working electrode and the counter electrode were placed in a third solution, and a current density current of 10 mA/cm 2 was applied to the working electrode to carry out electrochemical polymerization to obtain a conductive polymer material.
  • the method for preparing the electrode refers to the embodiment 1.
  • the initial capacity is 352 F/g
  • the capacity still retains 320 after 1000 cycles. F/g.
  • the graphene was dried in a dry box for 24 hours, and then placed in a reactor, and dried nitrogen gas was introduced for 0.5 h, and then a fluorine-fluorine mixed gas containing 30% of the total volume of fluorine gas was introduced, and the reaction was carried out at 250 ° C for 86 hours.
  • the fluorinated graphene is ultrasonically oscillated in a solution of 0.25 mol/L of dodecylbenzenesulfonic acid for 110 min to obtain a first solution of fluorinated graphene mass percentage of 0.025%;
  • the concentration of the aniline monomer is 0.25 mol/L, to obtain a second solution; adding potassium chloride to the second solution to make the potassium chloride concentration 0.1 mol/L, and obtaining the first Three solutions;
  • the working electrode and the counter electrode were placed in a third solution, and a current density current of 10 mA/cm 2 was applied to the working electrode to carry out electrochemical polymerization to obtain a conductive polymer material.
  • the method for preparing the electrode is as follows. When the initial capacity is 349 F/g, the capacity is still maintained after 1000 cycles. F/g.
  • the graphene was dried in a dry box for 24 hours, placed in a reactor, and subjected to dry nitrogen for 0.5 h, and then a fluorine-containing gas mixture containing fluorine gas in a total volume of 10% was introduced, and the reaction was carried out at 450 ° C. h, obtaining fluorinated graphene;
  • the fluorinated graphene was ultrasonically oscillated in a solution of 0.6 mol/L of dodecylbenzenesulfonic acid for 15 min to obtain a first solution of 0.01% by mass of the graphene fluoride mass percentage;
  • the working electrode and the counter electrode were placed in a third solution, and a current density current of 10 mA/cm 2 was applied to the working electrode to carry out electrochemical polymerization to obtain a conductive polymer material.
  • the method for preparing the electrode is as follows. When the initial capacity is 354 F/g, the capacity is still 340 after 1000 cycles. F/g.
  • the graphene was dried in a dry box for 24 hours, and then placed in a reactor, and dried nitrogen gas was introduced for 0.5 h, and then a fluorine-fluorine mixed gas containing 10% of the total volume of fluorine gas was introduced, and the reaction was carried out at 50 ° C for 120 hours.
  • the fluorinated graphene was ultrasonically shaken in a 0.1 mol/L solution containing dodecylbenzenesulfonic acid for 2 hours to obtain a mass percentage of fluorinated graphene. 1% of the first solution;
  • the aniline monomer is added to the first solution such that the concentration of the aniline monomer is 0. 1 mol / L, a second solution is obtained; potassium chloride is added to the second solution to make the potassium chloride concentration 0.025 mol / L, to obtain a third solution;
  • the working electrode and the counter electrode were placed in a third solution, and a current density current of 0.1 mA/cm 2 was applied to the working electrode to carry out electrochemical polymerization to obtain a conductive polymer material.
  • the method for preparing the electrode is as follows. When the initial capacity is 355 F/g, the capacity is still 338 after 1000 cycles. F/g.
  • the graphene was dried in a dry box for 24 hours, placed in a reactor, and subjected to dry nitrogen for 0.5 h, and then a fluorine-containing gas mixture containing 15% of the total volume of fluorine gas was introduced, and the reaction was carried out at 500 ° C. h, obtaining fluorinated graphene;
  • the fluorinated graphene was ultrasonically shaken in a solution of 0.45 mol/L of dodecylbenzenesulfonic acid for 1 hour to obtain a mass percentage of fluorinated graphene. 06% of the first solution;
  • the concentration of the aniline monomer is 0.45 mol/L, to obtain a second solution; adding potassium chloride to the second solution to make the potassium chloride concentration 0.3 mol/L, and obtaining the first Three solutions;
  • the working electrode and the counter electrode were placed in a third solution, and a current density current of 7 mA/cm 2 was applied to the working electrode to carry out electrochemical polymerization to obtain a conductive polymer material.
  • the method for preparing the electrode is as follows. When the initial capacity is 375 F/g, the capacity is still 359 after 1000 cycles. F/g.
  • the graphene was dried in a dry box for 24 hours, placed in a reactor, and subjected to dry nitrogen for 0.5 h, and then a fluorine-containing gas mixture containing fluorine gas in a total volume of 17% was introduced, and the reaction was carried out at 150 ° C. h, obtaining fluorinated graphene;
  • the first solution of the fluorinated graphene mass percentage of 0.08% is obtained by ultrasonically oscillating the solution of the fluorinated graphene in a solution of 0.035 mol/L;
  • the concentration of the aniline monomer is 0.035 mol/L, to obtain a second solution; adding potassium chloride to the second solution to make the potassium chloride concentration 0.3 mol/L, the first Three solutions;
  • the working electrode and the counter electrode were placed in a third solution, and a current density current of 7 mA/cm 2 was applied to the working electrode to carry out electrochemical polymerization to obtain a conductive polymer material.
  • the method for preparing the electrode is as follows. When the initial capacity is 382 F/g, the capacity is still 374 after 1000 cycles. F/g.

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Description

[根据细则37.2由ISA制定的发明名称]　导电高分子材料及其制备方法和应用 技术领域
本发明属于高分子材料技术领域，尤其涉及一种导电高分子材料、其制备方法和应用。
背景技术
导电聚合物是由一些碳骨架具有大共轭π键结构的导电聚合物，经化学或电化学掺杂后形成的导电率可以从绝缘体延伸到导体范围的一类高分子材料。导电高分子材料具有导电性能良好、制备方法简单，存放时间长久的优点，但是，现有的导电高分子材料循环稳定性能较差，在应用的过程中容易出现不稳定现象。
技术问题
有鉴于此，本发明实施例提供一种导电高分子材料，解决现有技术中导电高分子材料循环性能差的技术问题。本发明实施例进一步提供一种导电高分子材料制备方法。本发明实施例还提供上述导电高分子材料在太阳能电池、有机电致发光器件或锂离子电池中的应用。
技术解决方案
本发明是这样实现的，
一种导电高分子材料，包括导电聚合物和掺杂在该导电聚合物之中的氟化石墨烯，该导电聚合物和氟化石墨烯质量比为1:0.05-1，该导电聚合物为聚噻吩或其衍生物、聚吡咯或其衍生物以及聚苯胺或其衍生物中的一种。
本发明实施例进一步提供的一种导电高分子材料制备方法包括如下步骤：
将氟化石墨烯溶于含表面活性剂的溶液中，得到第一溶液；
按有机单体和该氟化石墨烯质量比1：0.05-1将有机单体加入至该第一溶液中，加入电解质，放置工作电极和对电极，通电进行电化学聚合，得到导电高分子材料，其中，该有机单体为苯胺或其衍生物、吡咯或其衍生物以及噻吩或其衍生物中的一种。
本发明实施例还提供上述导电高分子材料在太阳能电池、有机电致发光器件或锂离子电池中的应用。
 有益效果
本发明实施例导电高分子材料，通过掺杂氟化石墨烯，使其循环稳定性能大大增强，同时，该导电聚合物使其具有优异的容量性能。本发明实施例制备方法，操作简单，成本低廉，对设备要求低，适于工业化生产。
附图说明
图1是本发明实施例导电高分子材料在1mol/L的硫酸中循环寿命图。
本发明的最佳实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
一种导电高分子材料，包括导电聚合物和掺杂在该导电聚合物之中的氟化石墨烯，该导电聚合物和氟化石墨烯质量比为1:0.05-1，该导电聚合物为聚噻吩或其衍生物、聚吡咯或其衍生物以及聚苯胺或其衍生物中的一种。
本发明实施例导电高分子材料，包括氟化石墨烯，以及聚噻吩或其衍生物、聚吡咯或其衍生物，或者聚苯胺中或其衍生物的一种。氟化石墨烯具有良好的循环稳定性能，能够大大增加本发明实施例导电高分子材料的循环稳定性能，增长其使用期限；同时，上述导电聚合物具有优异的容量性能，使得本发明实施例导电高分子化合物具有较高的容量。
进一步，氟化石墨烯具有优异的导电性能，通过掺杂氟化石墨烯，使得本发明实施例导电高分子材料的导电性能得到显著增强。
具体地，该导电聚合物和氟化石墨烯的质量比为1:0.05-1，优选1:0.5-1。该氟化石墨烯掺杂在该导电聚合物之中；在一些具体实施例中，导电聚合物长链形成网状结构，该氟化石墨烯位于该网状结构之中，即该导电聚合物将氟化石墨烯包围。
本发明实施例进一步提供一种导电高分子材料制备方法，包括如下步骤：
S01，制备第一溶液：
将氟化石墨烯溶于含表面活性剂的溶液中，得到第一溶液；
S02，制备高分子材料；
按有机单体和氟化石墨烯质量比1：0.05-1将有机单体加入至该第一溶液中，加入电解质，放置工作电极和对电极，通电进行电化学聚合，得到导电高分子材料。
具体地，在S01步骤中，
该表面活性剂为阴离子表面活性剂、阳离子表面活性剂或非离子型表面活性剂或者两性表面活性剂。该阴离子表面活性剂选自烷基苯磺酸盐、脂肪醇硫酸盐、磷酸酯、十二烷基苯磺酸钠或甲基苯磺酸钠；该阳离子表面活性剂选自脂肪胺、胺氧化物、季铵盐或氯化四乙基铵；该非离子型表面活性剂选自脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、羧酸酯或脂肪醇酰胺；该两性活性剂选自咪唑啉。
进一步，该含有表面活性剂的溶液中表面活性剂的浓度为0.01-0.6mol/L，所使用的溶剂为水或其他溶剂。按氟化石墨烯质量分数为0.01-0.1%将氟化石墨烯溶于该含表面活性剂的溶液，然后超声振荡5分钟-2小时，得到第一溶液。氟化石墨烯和表面活性剂之间具有相容性，采用含表面活性剂的溶液作为氟化石墨烯的溶剂，能够保证氟化石墨烯被完全溶解、分散。
具体地，本发明实施例制备方法中使用的氟化石墨烯没有限制，可以为市售的氟化石墨烯，也可以为自制的氟化石墨烯。优选采用自制氟化石墨烯，制备过程如下：
无水无氧条件下，将石墨烯加入至反应器，通入氟气或氟气与惰性气体组成的混合气体，于50-500℃温度下反应3-120h，得到氟化石墨烯。该惰性气体是指氮气、氦气、氩气及氖气等。优选的，向反应器中通入的氟氮混合气体，氟气占混合气体体积的10-30%，氮作为氟的稀释气体。最优选为通入氟气占总体积20% 的氟氮混合气体，在250℃反应6h。该无氧条件没有限制，保证整个反应过程中没有氧气的存在即可，优选的，在通入氟气前，往反应器中通入氮气、氩气或氦气0.5-4小时，然后在密封条件下，通入上述反应气体；无水条件，即在反应前将石墨烯干燥，同时通入经过干燥的氟气或氟气与惰性气体的混合气体。
具体地，S02步骤中，
该有机单体是指噻吩或其衍生物、苯胺或其衍生物、吡咯或其衍生物。该有机单体加入至第一溶液中得到第二溶液，在该第二溶液中，有机单体浓度为0.01-0.6mol/L，有机单体和氟化石墨烯的质量比为1:0.01-1。
该电解质加入至第二溶液中，该电解质没有限制，能够溶于上述第二溶液并且导电即可，例如，氯化钾、氯化钠、氯酸钾、高氯酸钾、溴化钠、溴化钾、碘化钾、碘化钠、硝酸钾、硝酸钠或硫酸钠中一种或以上。加入该电解质后，得到第三溶液，第三溶液中电解质的浓度为0.001-0.3 mol/L。
然后，将工作电极和对电极置于该第三溶液中，向工作电极施加0.1-10 mA/cm2电流密度的电流进行电化学聚合反应，上述有机单体在电场作用下聚合，生成长链导电聚合物，大量该长链导电聚合物聚集形成网状结构或其他结构，进一步，该网状结构将氟化石墨烯包围，氟化石墨烯均匀掺杂在导电聚合物之间，在工作电极上形成均匀的复合膜，即导电高分子材料。通过控制聚合过程中通入电流的电量，可以控制高分子材料复合膜的厚度。
进一步地，该工作电极可以作为超级电容器电极板的基材，形成有导电高分子材料复合膜的工作电极可直接作为超级电容器电极。
该工作电极和对电极的材质没有限制。
本发明实施例通过电化学聚合方法制备导电高分子材料，使该高分子材料中导电聚合物和氟化石墨烯之间更加均匀的掺杂，从而大大提高导电高分子材料的导电性能和循环稳定性能。
本发明实施例导电高分子材料，通过掺杂氟化石墨烯，使其循环稳定性能大大增强，同时，该导电聚合物使其具有优异的容量性能。本发明实施例制备方法，操作简单，成本低廉，对设备要求低，适于工业化生产。
本发明实施例进一步提供上述导电高分子材料在太阳能电池、有机电致发光器件、锂离子电池中的应用。
以下结合具体实施例对本发明实施例制备方法进行详细阐述。
实施例一
(1) 制备氟化石墨烯
将石墨烯放入干燥箱中干燥24小时，再放入至反应器，通入干燥的氮气0.5h，然后通入氟气，在300℃下反应12h，得到氟化石墨烯；
(2) 制备第一溶液
将该氟化石墨烯在0.5mol/L的含十二烷基苯磺酸的溶液中超声振荡30min，制得氟化石墨烯质量百分数0.035%的第一溶液；
(3) 制备导电高分子材料
向第一溶液中加入噻吩单体，使噻吩单体的浓度为0.5mol/L，得到第二溶液；向第二溶液中加入氯化钾，使氯化钾浓度为0.3mol/L，得到第三溶液；
将工作电极和对电极置于第三溶液中，向工作电极施加10 mA/cm2电流密度电流，进行电化学聚合反应，得到导电高分子材料。
将得到的导电高分子材料与导电剂、粘结剂进行充分混合，然后涂在泡沫镍上，烘烤后制成电极，再将两片同样的电极组装成对称型电容器进行恒电流充放电测试，请参阅图1，图1显示本发明采用实施例1制备的导电高分子材料制成的电极在1mol/L的硫酸中循环寿命图，测试条件：电流密度为0.2A/g，截止电压范围0-1V，循环1000次。从图1中可看出，当初始容量为372F/g，1000次循环以后容量仍保有350 F/g，本发明实施例导电高分子材料具有优异的循环稳定性能。
实施例二
(1) 制备氟化石墨烯
将石墨烯放入干燥箱中干燥24小时，再放入至反应器，通入干燥的氮气0.5h，然后通入氟气占总体积20%的氟氮混合气体，在100℃下反应75h，得到氟化石墨烯；
(2) 制备第一溶液
将该氟化石墨烯在0.01mol/L的含十二烷基苯磺酸的溶液中超声振荡5min，制得氟化石墨烯质量百分数0.056%的第一溶液；
(3) 制备导电高分子材料
向第一溶液中加入吡咯单体，使吡咯单体的浓度为0.01mol/L，得到第二溶液；向第二溶液中加入硝酸钾，使硝酸钾浓度为0.02mol/L，得到第三溶液；
将工作电极和对电极置于第三溶液中，向工作电极施加10 mA/cm2电流密度电流，进行电化学聚合反应，得到导电高分子材料。
制备电极的方法参照实施例1，当初始容量为352F/g，1000次循环以后容量仍保有320 F/g。
实施例三
(1) 制备氟化石墨烯
将石墨烯放入干燥箱中干燥24小时，再放入至反应器，通入干燥的氮气0.5h，然后通入氟气占总体积30%的氟氦混合气体，在250℃下反应86h，得到氟化石墨烯；
(2) 制备第一溶液
将该氟化石墨烯在0.25mol/L的含十二烷基苯磺酸的溶液中超声振荡110min，制得氟化石墨烯质量百分数0.025%的第一溶液；
(3) 制备导电高分子材料
向第一溶液中加入苯胺单体，使苯胺单体的浓度为0.25mol/L，得到第二溶液；向第二溶液中加入氯化钾，使氯化钾浓度为0.1mol/L，得到第三溶液；
将工作电极和对电极置于第三溶液中，向工作电极施加10 mA/cm2电流密度电流，进行电化学聚合反应，得到导电高分子材料。
制备电极的方法参照实施例1，当初始容量为349F/g，1000次循环以后容量仍保有337 F/g。
实施例四
(1) 制备氟化石墨烯
将石墨烯放入干燥箱中干燥24小时，再放入至反应器，通入干燥的氮气0.5h，然后通入氟气占总体积10%的氟氦混合气体，在450℃下反应45 h，得到氟化石墨烯；
(2) 制备第一溶液
将该氟化石墨烯在0.6mol/L的含十二烷基苯磺酸的溶液中超声振荡15min，制得氟化石墨烯质量百分数0.01%的第一溶液；
(3) 制备导电高分子材料
向第一溶液中加入苯胺单体，使苯胺单体的浓度为0.6mol/L，得到第二溶液；向第二溶液中加入氯化钾，使氯化钾浓度为0.2mol/L，得到第三溶液；
将工作电极和对电极置于第三溶液中，向工作电极施加10 mA/cm2电流密度电流，进行电化学聚合反应，得到导电高分子材料。
制备电极的方法参照实施例1，当初始容量为354F/g，1000次循环以后容量仍保有340 F/g。
实施例五
(1) 制备氟化石墨烯
将石墨烯放入干燥箱中干燥24小时，再放入至反应器，通入干燥的氮气0.5h，然后通入氟气占总体积10%的氟氦混合气体，在50℃下反应120h，得到氟化石墨烯；
(2) 制备第一溶液
将该氟化石墨烯在0.1mol/L的含十二烷基苯磺酸的溶液中超声振荡2小时，制得氟化石墨烯质量百分数0. 1%的第一溶液；
(3) 制备导电高分子材料
向第一溶液中加入苯胺单体，使苯胺单体的浓度为0. 1mol/L，得到第二溶液；向第二溶液中加入氯化钾，使氯化钾浓度为0.025mol/L，得到第三溶液；
将工作电极和对电极置于第三溶液中，向工作电极施加0.1mA/cm2电流密度电流，进行电化学聚合反应，得到导电高分子材料。
制备电极的方法参照实施例1，当初始容量为355F/g，1000次循环以后容量仍保有338 F/g。
实施例六
(1) 制备氟化石墨烯
将石墨烯放入干燥箱中干燥24小时，再放入至反应器，通入干燥的氮气0.5h，然后通入氟气占总体积15%的氟氦混合气体，在500℃下反应3 h，得到氟化石墨烯；
(2) 制备第一溶液
将该氟化石墨烯在0.45mol/L的含十二烷基苯磺酸的溶液中超声振荡1小时，制得氟化石墨烯质量百分数0. 06%的第一溶液；
(3) 制备导电高分子材料
向第一溶液中加入苯胺单体，使苯胺单体的浓度为0.45mol/L，得到第二溶液；向第二溶液中加入氯化钾，使氯化钾浓度为0.3mol/L，得到第三溶液；
将工作电极和对电极置于第三溶液中，向工作电极施加7 mA/cm2电流密度电流，进行电化学聚合反应，得到导电高分子材料。
制备电极的方法参照实施例1，当初始容量为375F/g，1000次循环以后容量仍保有359 F/g。
实施例七
(1) 制备氟化石墨烯
将石墨烯放入干燥箱中干燥24小时，再放入至反应器，通入干燥的氮气0.5h，然后通入氟气占总体积17%的氟氦混合气体，在150℃下反应65 h，得到氟化石墨烯；
(2) 制备第一溶液
将该氟化石墨烯在0.035mol/L的含十二烷基苯磺酸的溶液中超声振荡15分钟，制得氟化石墨烯质量百分数0. 08%的第一溶液；
(3) 制备导电高分子材料
向第一溶液中加入苯胺单体，使苯胺单体的浓度为0.035mol/L，得到第二溶液；向第二溶液中加入氯化钾，使氯化钾浓度为0.3mol/L，得到第三溶液；
将工作电极和对电极置于第三溶液中，向工作电极施加7 mA/cm2电流密度电流，进行电化学聚合反应，得到导电高分子材料。
制备电极的方法参照实施例1，当初始容量为382F/g，1000次循环以后容量仍保有374 F/g。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种导电高分子材料，包括导电聚合物和掺杂在所述聚合物之中的氟化石墨烯，所述导电聚合物和氟化石墨烯质量比为1:0.05-1，所述导电导电聚合物为聚噻吩或其衍生物、聚吡咯或其衍生物以及聚苯胺或其衍生物中的一种。
  2. 如权利要求1所述的导电高分子材料，其特征在于，所述导电聚合物和氟化石墨烯的质量比为1:0.5-1。
  3. 一种导电高分子材料制备方法，包括如下步骤：
    将氟化石墨烯溶于含表面活性剂的溶液中，得到第一溶液；
    按有机单体和所述氟化石墨烯质量比1：0.05-1将有机单体加入至所述第一溶液中，加入电解质，放置工作电极和对电极，通电进行电化学聚合，得到导电高分子材料，所述有机单体为苯胺或其衍生物、吡咯或其衍生物以及噻吩或其衍生物中的一种。
  4. 如权利要求3所述的导电高分子材料制备方法，其特征在于，还包括如下制备氟化石墨烯的步骤：无水无氧条件下，将石墨烯加入至反应器，通入氟气或氟气与惰性气体组成的混合气体，于50-500 ℃温度下反应3-120 小时，得到氟化石墨烯。
  5. 如权利要求3所述的导电高分子材料制备方法，其特征在于，所述表面活性剂为阴离子表面活性剂、阳离子表面活性剂、非离子型表面活性剂或两性表面活性剂。
  6. 如权利要求5所述的导电高分子材料制备方法，其特征在于，所述工作电极为超级电容器电极板的基材。
  7. 如权利要求3所述的导电高分子材料制备方法，其特征在于，所述第一溶液中氟化石墨烯的质量分数为0.01-0.1%。
  8. 如权利要求3所述的导电高分子材料制备方法，其特征在于，所述有机单体加入至所述第一溶液后，所述有机单体浓度为0.01-0.6mol/L。
  9. 如权利要求3所述的导电高分子材料制备方法，其特征在于，所述电化学聚合过程中通入的电流密度为0.1-10 mA/cm2。
  10. 如权利要求1-2所述的导电高分子材料在太阳能电池、有机电致发光器件、锂离子电池或超级电容器中的应用。
PCT/CN2010/080512 2010-12-30 2010-12-30 导电高分子材料及其制备方法和应用 WO2012088691A1 (zh)

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