WO2017101795A1 - 双功能电极及其制备方法和应用 - Google Patents

双功能电极及其制备方法和应用 Download PDF

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WO2017101795A1
WO2017101795A1 PCT/CN2016/109989 CN2016109989W WO2017101795A1 WO 2017101795 A1 WO2017101795 A1 WO 2017101795A1 CN 2016109989 W CN2016109989 W CN 2016109989W WO 2017101795 A1 WO2017101795 A1 WO 2017101795A1
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layer
electrode
conductive polymer
capacitor
prepared
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PCT/CN2016/109989
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English (en)
French (fr)
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孙公权
王素力
付旭东
戚甫来
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中国科学院大连化学物理研究所
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Priority claimed from CN201510963958.5A external-priority patent/CN106898497A/zh
Priority claimed from CN201510961029.0A external-priority patent/CN106910641A/zh
Priority claimed from CN201510964138.8A external-priority patent/CN106898500A/zh
Application filed by 中国科学院大连化学物理研究所 filed Critical 中国科学院大连化学物理研究所
Publication of WO2017101795A1 publication Critical patent/WO2017101795A1/zh

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    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to the field of fuel cell and supercapacitor preparation, and more particularly to a bifunctional electrode capable of storing charge while an electrode reaction occurs.
  • the present invention also relates to a method of preparing the above dual function electrode.
  • the patent (CN102576613A) designs a fuel cell/supercapacitor/battery power system for vehicle propulsion. This system uses external recombination, and the circuit design is complicated, which increases the weight of the device and reduces the performance of the device.
  • cerium oxide is added to the electrode of a direct methanol fuel cell, and the dynamic performance of the battery is improved by the capacitance performance of cerium oxide due to the conductance of cerium oxide. Smaller, the amount of cerium oxide in the capacitor layer is smaller, the stored charge is less, and it cannot meet the working requirements of the supercapacitor, so it cannot be used as a dual-function electrode.
  • the object of the present invention is to prepare a dual-function electrode, which can catalyze the reaction of the electrode while storing electric energy, and discharge the stored electric energy for a short time when needed to achieve the purpose of instantaneous large current discharge.
  • a dual-function electrode comprising a base layer and a capacitance-catalytic composite layer attached to the base layer; the capacitance-catalytic composite layer containing a capacitor material, an electrocatalyst and a binder;
  • a capacitor layer containing a capacitor material is attached to a surface of one side of the base layer, and a catalytic layer containing an electrocatalyst is attached to the other side surface;
  • the capacitor layer comprising a base layer and a capacitor layer containing a capacitor material sequentially attached to the base layer and a catalytic layer containing an electrocatalyst; the capacitor layer being disposed between the base layer and the catalyst layer.
  • the base layer, the capacitor layer and the catalyst layer have different combinations: (1) the capacitor layer and the catalyst layer are on both sides of the diffusion layer; (2) the capacitor layer and the catalyst layer are on the same side of the base layer, and the capacitor layer is close to the base The bottom layer or the catalytic layer is in close proximity to the base layer; (3) the capacitor layer and the catalytic layer are uniformly mixed into a layer to form a capacitor-catalytic composite layer attached to the substrate layer.
  • the capacity of the electrocatalyst in the capacitance-catalytic composite layer is 0.05-5 mg/cm 2
  • the mass of the binder is 5%-50% of the total mass of the electrocatalyst and the binder
  • the loading capacity of the capacitor material is 0.1-50 mg. /cm 2 ;
  • the loading of the electrocatalyst in the catalytic layer is 0.05-5 mg/cm 2 ; the loading capacity of the capacitor material in the capacitor layer is 0.1-50 mg/cm 2 ; the catalytic layer contains a binder, The binder mass accounts for 5%-50% of the total mass of the electrocatalyst and binder.
  • the capacitive material is a conductive polymer; the base layer is one of carbon paper or carbon cloth.
  • the conductive polymer is polyaniline, polypyrrole, polythiophene, polyfluorene, polyheptaphthalene, polyglycy ring, polynaphthalene, polycarbazole, polyfluorene, poly(3,4-ethylenedioxythiophene) or Derivatives or copolymers between them One or more;
  • the binder is PTFE or
  • the preparation method of the dual-function electrode comprises (1) preparation of a capacitor material and (2) preparation of a capacitor-catalyzed composite layer; the capacitor material is prepared by preparing an electroconductive polymer by electrochemical method or chemical polymerization method;
  • electrochemically preparing a capacitive layer on one side of the substrate material or first preparing a conductive polymer by chemical polymerization, and then using one or more of brushing or spraying or screen printing a conductive polymer is prepared on one side surface of the base material; and (2) a catalytic layer is prepared on the other side surface of the base material by one or more of brush coating or spray coating or screen printing;
  • electrochemically preparing a capacitive layer on one side of the substrate material or first preparing a conductive polymer by chemical polymerization, and then using one or more of brushing or spraying or screen printing
  • the conductive polymer is prepared on one surface of the base material; and
  • the catalytic layer is prepared by using one or more of brush coating or spray coating or screen printing on the surface of the capacitor layer prepared in the step (1).
  • the capacitor material is prepared by an electrochemical method, in an electrolyte solution to which a doping acid or a conductive polymer monomer solution is added, a conductive substrate is used as a working electrode, a platinum sheet is a counter electrode, and a saturated calomel electrode is used.
  • a reference electrode electrochemically depositing a conductive polymer on the surface of the conductive substrate, and stripping the prepared conductive polymer from the conductive substrate to obtain a conductive polymer;
  • the conductive substrate component comprises platinum, gold, copper, One or more of silver;
  • the electrolyte solution is added with an acid-doped conductive polymer monomer solution, the base layer is used as a working electrode, the platinum sheet is a counter electrode, and the saturated calomel electrode is a reference electrode, electrochemically depositing a conductive polymer on a surface of one side of the base layer to prepare the capacitor layer;
  • a conductive polymer is prepared by a chemical polymerization method
  • a conductive polymer is prepared by adding a doping acid and an oxidizing agent to the conductive polymer monomer solution to cause chemical polymerization.
  • the solvent is one or a mixture of two or more of methanol, ethanol, water, ethylene glycol and isopropyl alcohol, and is electrically conductive.
  • the concentration of the polymer monomer is 0.001-2 mol/L;
  • the doping acid is one or a mixture of two or more of hydrochloric acid, sulfuric acid, perchloric acid, and nitric acid; and the concentration of the doping acid is 0.1- 2 mol/L;
  • the reaction temperature during the electrochemical deposition is -5 to 50 ° C, and the deposition current density is 0.01 to 20 mA/cm 2 .
  • the capacitor-catalytic composite layer is prepared by adding the conductive polymer obtained in the step (1) to the solvent, and preparing the slurry by using the electrocatalyst and the binder, and adopting one or more of brush coating, spray coating and screen printing. Forming a capacitance-catalytic composite layer on a surface of a gas diffusion layer;
  • the catalyst layer is prepared by adding a catalyst and a binder to a solvent;
  • the solvent is one or a mixture of two or more of water, ethanol, and ethylene glycol, and the concentration of the catalyst in the solvent is 0.1-5 mg/ml, the binder is added in proportion to form a catalyst slurry, which is one or more of spraying, brushing or screen printing.
  • the conductive polymer is polyaniline, polypyrrole, polythiophene, polyfluorene, poly-naphthalene, poly-glycine ring, polynaphthalene, polycarbazole, polyfluorene, poly(3, One or a mixture of two or more of 4-ethylenedioxythiophene) or a derivative thereof or a copolymer therebetween.
  • the solvent of the conductive polymer monomer solution is one or a mixture of two or more of methanol, ethanol, water, ethylene glycol and isopropyl alcohol, and conductive polymerization
  • concentration of the monomer is 0.001-2 mol/L
  • the doping acid is one or a mixture of two or more of hydrochloric acid, sulfuric acid, perchloric acid, and nitric acid
  • concentration of the doping acid is 0.1-2 mol.
  • the oxidizing agent is one or a mixture of two or more of ammonium persulfate, iron chloride, hydrogen peroxide, and potassium permanganate.
  • the dual-function electrode fuel cell-supercapacitor integrated power generation unit includes laminated layers in sequence An anode, an electrolyte membrane and a cathode, the anode and/or cathode being a bifunctional electrode; the electrolyte membrane being a proton exchange membrane or a basic anion exchange membrane;
  • the dual function electrode alone tests its performance as a half cell.
  • a catalytic layer in the dual function electrode is attached to the electrolyte membrane.
  • the catalytic layer is composed of a noble metal electrocatalyst or a non-precious metal electrocatalyst mixed binder.
  • the noble metal electrocatalyst is one or more of Pt/C, Pt black, PtRu/C, PtRu black, PtCo/C or PtCo black, and the noble metal loading is 0.05-5 mg/cm 2 .
  • the non-noble metal electrocatalyst is a nitrogen-doped carbon catalyst, an iron-nitrogen-doped carbon catalyst, a manganese oxide catalyst, a cobalt oxide catalyst or a silver catalyst, and has a catalyst loading of 0.5-10 mg/cm 2 .
  • the binder is Or Teflon.
  • the different combinations of the bifunctional electrodes are prepared as follows.
  • Electrochemical polymerization method in an electrolyte solution containing a doped acid or a conductive polymer monomer solution, a conductive substrate is used as a working electrode, a platinum plate is a counter electrode, a saturated calomel electrode is a reference electrode, and an electrolyte
  • the solvent is one or a mixture of two or more of methanol, ethanol, water, ethylene glycol, and isopropyl alcohol, and the concentration of the conductive polymer monomer is 0.001 to 2 mol/L;
  • the doping acid is hydrochloric acid, a mixed acid of one or more of sulfuric acid, perchloric acid, and nitric acid; the concentration of the doping acid is 0.1-2 mol/L; and the reaction temperature during the electrochemical polymerization is -5-50 ° C, electricity
  • the current density of the polymerization was 0.01-20 mA/cm 2 .
  • a conductive polymer is prepared by adding a doping acid and an oxidizing agent to a conductive polymer monomer solution to chemically polymerize it.
  • the solvent of the conductive polymer monomer solution is one or a mixture of two or more of methanol, ethanol, water, ethylene glycol, isopropyl alcohol, and the concentration of the conductive polymer monomer is 0.001-2 mol/L;
  • the doping acid is one or a mixture of two or more of hydrochloric acid, sulfuric acid, perchloric acid, and nitric acid; the concentration of the doping acid is 0.1-2 mol/L; in the chemical polymerization method, in a solution
  • the ratio of the amount of the oxidizing agent to the conductive polymer monomer is 0.5-2; the reaction temperature is -5 to 50 ° C, and the reaction time is 12 to 48 hours; the oxidizing agent is ammonium persulfate, iron chloride, One or a mixture of two or more of hydrogen peroxide and
  • the conductive polymer is prepared in the same manner as in (a) (b) of the combination mode (1), and then the electrocatalyst slurry is sprayed or brushed on the surface of the capacitor layer on the substrate layer, or the capacitor is prepared on the surface of the catalyst layer on the substrate layer.
  • Floor is prepared in the same manner as in (a) (b) of the combination mode (1), and then the electrocatalyst slurry is sprayed or brushed on the surface of the capacitor layer on the substrate layer, or the capacitor is prepared on the surface of the catalyst layer on the substrate layer.
  • Conductive polymer is prepared by electrochemical polymerization on platinum, gold, copper, silver as a substrate, and then peeled off to obtain a conductive polymer powder, or a conductive polymer is prepared by a chemical polymerization method, and then mixed with an electrocatalyst to prepare a slurry. Spray or brush onto the diffusion layer.
  • the bifunctional electrode is used as the working electrode, the Pt piece is the counter electrode, and the saturated calomel electrode is the reference electrode.
  • the bifunctional electrode is tested for its performance in 0.5 mol/L sulfuric acid or 1 mol/L perchloric acid.
  • a composite power source is prepared by sequentially laminating an anode, an electrolyte membrane and a cathode, the anode and/or cathode being a bifunctional electrode; the electrolyte membrane being a proton exchange membrane or a basic anion exchange membrane, (1) a capacitor layer and a catalyst When the layer is on both sides of the substrate layer, the catalyst layer is attached to the electrolyte membrane; (2) the capacitor layer and the catalyst layer are on the same side of the substrate layer, and the capacitor layer is in close proximity to the substrate layer or the catalyst layer is adjacent to the substrate layer, a catalytic layer or a capacitor layer is attached to the electrolyte membrane; (3) the capacitor layer and the catalytic layer are uniformly mixed into a layer of a capacitor-catalytic composite layer attached to the substrate layer, the capacitor-catalytic composite layer and the electrolyte membrane Attached. Test the steady-state discharge characteristics of the composite power supply and pulse discharge Electrical characteristics.
  • the dual function electrode has the following advantages:
  • the charge of the active material can be stored in the capacitor material of the electrode, and when the passage is made, the charge is quickly released, and the current can be discharged by a large current;
  • the thickness of the capacitor layer or the capacitor-catalytic composite layer can be controlled, and the magnitude of the pulse current can be controlled by controlling the thickness of the capacitor layer;
  • the capacitor layer can simultaneously have the function of a microporous layer, which is a more balanced distribution of reactants
  • the conductive polymer can increase the connection between the catalysts and reduce the electronic resistance
  • the capacitor layer can improve the dynamic stability of the battery
  • the assembled battery has a simple structure and does not require external complicated control circuits.
  • 1 is a schematic view showing the structure of different dual-function electrodes; 1 is a base layer; 2 is a capacitor layer; 3 is a catalyst layer;
  • Figure 2 is a photomicrograph of polyaniline in Example 1;
  • Figure 3 is a photomicrograph of polyaniline in Example 2.
  • Figure 4 is a photomicrograph of polyaniline in Example 3.
  • Figure 5 is a photomicrograph of polyaniline in Example 4.
  • Figure 6 is a photo of a carbon cloth in Comparative Example 1;
  • Figure 7 is a bifunctional cathode of Example 1 and a comparative cathode cyclic voltammetry curve of Comparative Example 1;
  • Figure 8 is a polarization curve of the bifunctional cathode in Example 1 and the comparative cathode oxygen reduction reaction in Comparative Example 1;
  • Figure 9 is a constant current discharge curve of the bifunctional cathode of Example 1 and the comparative cathode of Comparative Example 1 at a current density of 5 mA cm -2 ;
  • Figure 10 is a constant current discharge curve of the dual function cathode of Example 1 and the comparative cathode of Comparative Example 1 at a current density of 40 mA cm -2 ;
  • FIG 11 is a dual-function cathode and Comparative Comparative 1 880mA cm -2 cathode to a current density of 980mA cm -2 pulse discharge curve of the embodiment;
  • Figure 12 shows the stability of the comparative cathode pulse discharge in the dual function cathode of Example 1 and Comparative Example 1;
  • Figure 13 is a bifunctional anode of Examples 5 and 6 and a comparative anode cyclic voltammetry curve of Comparative Example 2;
  • Figure 14 is a constant current discharge curve of the bifunctional anode of Examples 5 and 6 and the comparative anode of Comparative Example 2 at a current density of 80 mA cm -2 ;
  • Figure 15 is a pulse discharge curve of a 880 mA cm -2 current density in a bifunctional anode of Examples 5 and 6 and a comparative anode of Comparative Example 2;
  • Figure 16 shows the steady state discharge performance of the composite direct methanol fuel cell of Example 9 and the direct methanol fuel cell of Comparative Example 3;
  • Figure 17 is a pulse discharge performance of the composite direct methanol fuel cell of Example 9 and the direct methanol fuel cell of Comparative Example 3;
  • Figure 18 is a comparison of steady-state discharge performance and pulse discharge performance of the composite direct methanol fuel cell of Example 9 and the direct methanol fuel cell of Comparative Example 3;
  • Figure 19 is an electron micrograph of Example 13
  • Figure 20 is an electron micrograph of Comparative Example 4.
  • Figure 21 is a discharge curve of Example 14 at a current density
  • Figure 22 is an electron micrograph of a dual function cathodic capacitor layer prepared in Example 18;
  • Figure 23 shows the open circuit voltage of the bifunctional cathode prepared in Example 17; it can be seen from the figure that the voltage is lower when passing nitrogen gas, self-charging when oxygen is passed, the charge is stored on the electrode, the voltage rises with time, and then reaches one. Balance value;
  • Figure 24 is a graph showing the discharge curves of the cathodes of Comparative Example 4 and Examples 17, 18 at a current density of 25 mA/cm 2 . As can be seen from the figure, the cathodes prepared in Examples 17 and 18 exhibited significant capacitance properties;
  • Figure 25 is an electron micrograph of Example 22
  • Fig. 26 shows the open circuit voltages of the electrodes in Comparative Example 5 and Examples 21 and 22. As can be seen from the figure, the open circuit voltage becomes small due to the addition of polyaniline.
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a platinum plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the bifunctional cathode was tested by introducing high purity nitrogen into the solution.
  • the oxygen reduction reaction polarization curve of the bifunctional cathode was tested by introducing high purity oxygen into the solution; the constant current discharge curve at 5 mA cm -2 and 40 mA cm -2 current density was tested; the pulse discharge curve was tested and continued every 5 s. 10ms pulse discharge, each pulse discharge interval current increased by 20mA cm -2 ; test pulse discharge stability, every 5s for 0.5s pulse discharge, each pulse discharge current density is 5mA cm -2 , cycle 500 times .
  • aniline to a 1 mol/L aqueous solution of perchloric acid to make the concentration of aniline 0.5 mol/L, carbon cloth (2 ⁇ 2 cm 2 ) as the working electrode, platinum plate as the counter electrode, and saturated calomel electrode as the reference electrode.
  • the polymerization temperature is 25 ° C
  • the polyaniline is prepared by electropolymerization at a current density of 0.03 mA/cm 2 to a loading of 10 mg/cm 2 .
  • the prepared polyaniline electron micrograph is as shown in FIG. 3 , which can be It can be seen that the polyaniline nanowires are evenly distributed around the carbon fibers in the carbon cloth.
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a platinum plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the bifunctional cathode was tested by introducing high purity nitrogen into the solution.
  • the oxygen reduction reaction polarization curve of the bifunctional cathode was tested by introducing high purity oxygen into the solution; the constant current discharge curve at 5 mA cm -2 and 40 mA cm -2 current density was tested; the pulse discharge curve was tested and continued every 5 s. 10ms pulse discharge, each pulse discharge interval current increased by 20mA cm -2 ; test pulse discharge stability, every 5s for 0.5s pulse discharge, each pulse discharge current density is 5mA cm -2 , cycle 500 times .
  • aniline to a 1 mol/L aqueous solution of perchloric acid to make the concentration of aniline 0.5 mol/L, carbon cloth (2 ⁇ 2 cm 2 ) as the working electrode, platinum plate as the counter electrode, and saturated calomel electrode as the reference electrode.
  • the polymerization temperature is 25 ° C
  • the polyaniline is prepared by electropolymerization at a current density of 0.03 mA/cm 2 to a loading of 1 mg/cm 2 .
  • the prepared polyaniline electron micrograph is as shown in FIG. 4 , which can be It can be seen that the polyaniline nanowires are evenly distributed around the carbon fibers in the carbon cloth.
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a platinum plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the bifunctional cathode was tested by introducing high purity nitrogen into the solution.
  • the oxygen reduction reaction polarization curve of the bifunctional cathode was tested by introducing high purity oxygen into the solution; the constant current discharge curve at 5 mA cm -2 and 40 mA cm -2 current density was tested; the pulse discharge curve was tested and continued every 5 s. 10ms pulse discharge, each pulse discharge interval current increased by 20mA cm -2 ; test pulse discharge stability, every 5s for 0.5s pulse discharge, each pulse discharge current density is 5mA cm -2 , cycle 500 times .
  • aniline to a 1 mol/L aqueous solution of perchloric acid to make the concentration of aniline 0.5 mol/L, carbon cloth (2 ⁇ 2 cm 2 ) as the working electrode, platinum plate as the counter electrode, and saturated calomel electrode as the reference electrode.
  • the polymerization temperature is 25 ° C
  • the polyaniline is prepared by electropolymerization at a current density of 0.03 mA/cm 2 to a loading of 0.1 mg/cm 2 .
  • the prepared polyaniline electron micrograph is as shown in FIG. 5 , from the figure. It can be seen that the polyaniline nanowires are evenly distributed around the carbon fibers in the carbon cloth.
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a platinum plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the bifunctional cathode was tested by introducing high purity nitrogen into the solution.
  • the oxygen reduction reaction polarization curve of the bifunctional cathode was tested by introducing high purity oxygen into the solution; the constant current discharge curve at 5 mA cm -2 and 40 mA cm -2 current density was tested; the pulse discharge curve was tested and continued every 5 s. 10ms pulse discharge, each pulse discharge interval current increased by 20mA cm -2 ; test pulse discharge stability, every 5s for 0.5s pulse discharge, each pulse discharge current density is 5mA cm -2 , cycle 500 times .
  • aniline to a 1 mol/L aqueous solution of perchloric acid to make the concentration of aniline 0.5 mol/L, carbon cloth (2 ⁇ 2 cm 2 ) as the working electrode, platinum plate as the counter electrode, and saturated calomel electrode as the reference electrode.
  • the polymerization temperature was 25 °C, in the manufacture of electrical current density of polymerization of polyaniline 0.03mA / cm 2, making loading of 50mg / cm 2; formulated catalyst slurry 75% PtRu / C, wherein PtRu concentration of 1mg / mL, 15% of the total solid mass, the catalyst slurry was sprayed on polyaniline so that the loading of PtRu was 2 mg/cm 2 .
  • the performance of the bifunctional anode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional anode as the working electrode, a platinum plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the bifunctional anode was tested by introducing high purity nitrogen into the solution. Methanol was added to the solution to make the methanol concentration 0.5 mol/L, and the constant current discharge curve at a current density of 80 mA cm -2 was tested; the pulse discharge curve was tested, and a pulse discharge of 10 ms was performed every 5 s, and each pulse discharge interval was performed. The current is increased by 20mA cm -2 .
  • An aniline was added to a 1 mol/L aqueous solution of perchloric acid to give an aniline concentration of 0.5 mol/L, a carbon cloth (2 ⁇ 2 cm 2 ) as a working electrode, a platinum plate as a counter electrode, and a saturated calomel electrode as a reference.
  • the electrode was polymerized at a temperature of 25 ° C, and polyaniline was prepared by electropolymerization at a current density of 0.03 mA/cm 2 to a loading of 10 mg/cm 2 ; a catalyst slurry of 75% PtRu/C was prepared, wherein the PtRu concentration was 1 mg/mL. , 15% of the total solid mass, the catalyst slurry was sprayed on polyaniline so that the loading of PtRu was 2 mg/cm 2 .
  • the performance of the bifunctional anode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional anode as the working electrode, a platinum plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the bifunctional anode was tested by introducing high purity nitrogen into the solution. Methanol was added to the solution to make the methanol concentration 0.5 mol/L, and the constant current discharge curve at a current density of 80 mA cm -2 was tested; the pulse discharge curve was tested, and a pulse discharge of 10 ms was performed every 5 s, and each pulse discharge interval was performed. The current is increased by 20mA cm -2 .
  • aniline to a 1 mol/L aqueous solution of perchloric acid to make the concentration of aniline 0.5 mol/L, carbon cloth (2 ⁇ 2 cm 2 ) as the working electrode, platinum plate as the counter electrode, and saturated calomel electrode as the reference electrode.
  • the polymerization temperature was 25 ° C
  • polyaniline was prepared by electropolymerization at a current density of 0.03 mA/cm 2 to a loading of 1 mg/cm 2 ; a catalyst slurry of 75% PtRu/C was prepared, wherein the PtRu concentration was 1 mg/mL, 15% of the total solid mass, the catalyst slurry was sprayed on polyaniline so that the loading of PtRu was 2 mg/cm 2 .
  • the performance of the bifunctional anode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional anode as the working electrode, a platinum plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the bifunctional anode was tested by introducing high purity nitrogen into the solution. Methanol was added to the solution to make the methanol concentration 0.5 mol/L, and the constant current discharge curve at a current density of 80 mA cm -2 was tested; the pulse discharge curve was tested, and a pulse discharge of 10 ms was performed every 5 s, and each pulse discharge interval was performed. The current is increased by 20mA cm -2 .
  • aniline to a 1 mol/L aqueous solution of perchloric acid to make the concentration of aniline 0.5 mol/L, carbon cloth (2 ⁇ 2 cm 2 ) as the working electrode, platinum plate as the counter electrode, and saturated calomel electrode as the reference electrode.
  • the polymerization temperature was 25 ° C
  • polyaniline was prepared by electropolymerization at a current density of 0.03 mA/cm 2 to a loading of 0.1 mg/cm 2 ; a catalyst slurry of 75% PtRu/C was prepared, wherein the PtRu concentration was 1 mg/mL. , 15% of the total solid mass, the catalyst slurry was sprayed on polyaniline so that the loading of PtRu was 2 mg/cm 2 .
  • the performance of the bifunctional anode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional anode as the working electrode, a platinum plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the bifunctional anode was tested by introducing high purity nitrogen into the solution. Methanol was added to the solution to make the methanol concentration 0.5 mol/L, and the constant current discharge curve at a current density of 80 mA cm -2 was tested; the pulse discharge curve was tested, and a pulse discharge of 10 ms was performed every 5 s, and each pulse discharge interval was performed. The current is increased by 20mA cm -2 .
  • the 115 film was an electrolyte membrane, and the bifunctional cathode of Example 1 and the bifunctional anode of Example 5 were assembled into a composite MEA, and the effective area of the electrode was 1 cm 2 .
  • the battery temperature was 80 ° C
  • the anode 0.5 mol / L methanol aqueous solution was fed
  • the flow rate was 1 mL / min
  • the anode air was fed
  • the flow rate was 80 mL / min.
  • the steady-state discharge performance and transient discharge performance of the composite direct methanol fuel cell were tested.
  • the 115 film was an electrolyte membrane, and the bifunctional cathode of Example 2 and the bifunctional anode of Example 6 were assembled into a composite MEA, and the effective area of the electrode was 1 cm 2 .
  • the battery temperature was 80 ° C
  • the anode 0.5 mol / L methanol aqueous solution was fed
  • the flow rate was 1 mL / min
  • the anode air was fed
  • the flow rate was 80 mL / min.
  • the steady-state discharge performance and transient discharge performance of the composite direct methanol fuel cell were tested.
  • the 115 film was an electrolyte membrane, and the bifunctional cathode of Example 3 and the bifunctional anode of Example 7 were assembled into a composite MEA, and the effective area of the electrode was 1 cm 2 .
  • the battery temperature was 80 ° C
  • the anode 0.5 mol / L methanol aqueous solution was fed
  • the flow rate was 1 mL / min
  • the anode air was fed
  • the flow rate was 80 mL / min.
  • the steady-state discharge performance and transient discharge performance of the composite direct methanol fuel cell were tested.
  • the 115 film was an electrolyte membrane, and the bifunctional cathode of Example 4 and the bifunctional anode of Example 8 were assembled into a composite MEA, and the effective area of the electrode was 1 cm 2 .
  • the battery temperature was 80 ° C
  • the anode 0.5 mol / L methanol aqueous solution was fed
  • the flow rate was 1 mL / min
  • the anode air was fed
  • the flow rate was 80 mL / min.
  • the steady-state discharge performance and transient discharge performance of the composite direct methanol fuel cell were tested.
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested.
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode. Test the open circuit voltage of a dual function cathode in nitrogen and oxygen And the discharge curve in oxygen.
  • the aniline was chemically polymerized in a 1 mol/L aqueous solution of perchloric acid, the concentration of aniline was 10 mmol/L, the concentration of ammonium persulfate was 6.7 mmol/L, and the reaction was carried out at 0-5 ° C for 24 hours, filtered and dried.
  • Polyaniline sample polyaniline slurry was prepared, the concentration of polyaniline was 0.67 mg/mL, and the slurry was sprayed on the side of the carbon cloth to make the loading of polyaniline 0.2 mg/cm 2 ; prepared with 60% Pt/C catalyst. In the catalyst slurry, the Pt in the catalyst slurry is 1 mg/mL. 20% of the total solid mass, the slurry was sprayed onto the polyaniline layer so that the loading of Pt was 0.3 mg/cm 2 .
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested.
  • the aniline was chemically polymerized in a 1 mol/L aqueous solution of perchloric acid, the concentration of aniline was 10 mmol/L, the concentration of ammonium persulfate was 6.7 mmol/L, and the reaction was carried out at 0-5 ° C for 24 hours, filtered and dried.
  • Polyaniline sample polyaniline slurry was prepared, the concentration of polyaniline was 0.67mg/mL, the slurry was sprayed on the side of the carbon cloth to make the loading of polyaniline 2mg/cm 2 ; and the catalyst was prepared by 60% Pt/C catalyst.
  • the catalyst slurry has a Pt of 1 mg/mL. 20% of the total solid mass, the slurry was sprayed onto the polyaniline layer so that the loading of Pt was 0.3 mg/cm 2 .
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested.
  • the loading was 0.2 mg/cm 2 , and then 60% Pt/C catalyst slurry was sprayed on the other side of the carbon cloth, and the Pt in the catalyst slurry was 1 mg/mL. It accounts for 20% of the total solid mass, and the loading of Pt on the carbon cloth is 0.3 mg/cm 2 .
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested.
  • the open circuit voltage in nitrogen and oxygen is shown in Fig. 23. It can be seen that the voltage is lower when passing nitrogen gas, self-charging when oxygen is passed, the charge is stored on the electrode, the voltage rises with time, and then reaches an equilibrium value. As shown in Fig. 24, when discharging at a current density of 25 mA/cm 2 , the voltage decay was slower than that of the comparative cathode of Comparative Example 1.
  • the loading capacity is 2 mg/cm 2 , and then 60% Pt/C catalyst slurry is sprayed on the other side of the carbon cloth, and the Pt in the catalyst slurry is 1 mg/mL. It accounts for 20% of the total solid mass, and the loading of Pt on the carbon cloth is 0.3 mg/cm 2 .
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested.
  • the electron micrograph of the capacitor layer and the performance of the electrode are shown in Fig. 22 and Fig. 24, respectively. When discharging at a current density of 25 mA/cm 2 , the voltage decay is slower than that of the comparative cathode of Comparative Example 1, showing a good capacitance effect. .
  • the aniline was chemically polymerized in a 1 mol/L aqueous solution of perchloric acid, the concentration of aniline was 10 mmol/L, the concentration of ammonium persulfate was 6.7 mmol/L, and the reaction was carried out at 0-5 ° C for 24 hours, filtered and dried.
  • a polyaniline sample was prepared, and a polyaniline slurry was prepared. The concentration of polyaniline was 0.67 mg/mL, and the slurry was sprayed onto the surface of one side of the carbon cloth to make the loading of polyaniline 0.2 mg/cm 2 ; 60% Pt/C catalyst. Prepare a catalyst slurry with a Pt of 1 mg/mL in the catalyst slurry. 20% of the total solid mass, the slurry was sprayed onto the other side of the carbon cloth so that the loading of Pt was 0.3 mg/cm 2 .
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested.
  • the aniline was chemically polymerized in a 1 mol/L aqueous solution of perchloric acid, the concentration of aniline was 10 mmol/L, the concentration of ammonium persulfate was 6.7 mmol/L, and the reaction was carried out at 0-5 ° C for 24 hours, filtered and dried.
  • Polyaniline sample polyaniline slurry was prepared, the concentration of polyaniline was 0.67mg/mL, and the slurry was sprayed onto the surface of carbon cloth to make the loading of polyaniline 2mg/cm 2 ; prepared with 60% Pt/C catalyst.
  • the Pt in the catalyst slurry is 1 mg/mL. 20% of the total solid mass, the slurry was sprayed onto the other side of the carbon cloth so that the loading of Pt was 0.3 mg/cm 2 .
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested.
  • aniline was added to a 1 mol/L aqueous solution of perchloric acid to make the concentration of aniline 0.5 mol/L
  • the conductive substrate was used as the working electrode
  • the platinum plate was the counter electrode
  • the saturated calomel electrode was the reference electrode
  • the reaction temperature was 0- At 5 ° C
  • the aniline was electropolymerized at a current density of 0.04 mA/cm 2 , and the polyaniline on the electrode was scraped off and washed to obtain a polyaniline sample
  • the catalyst slurry was prepared with a 60% Pt/C catalyst, and the Pt of the catalyst slurry was 1 mg.
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested. As shown in Figure 26, the open circuit voltage of this electrode is lower than that of the comparative example.
  • aniline was added to a 1 mol/L aqueous solution of perchloric acid to make the concentration of aniline 0.5 mol/L
  • the conductive substrate was used as the working electrode
  • the platinum plate was the counter electrode
  • the saturated calomel electrode was the reference electrode
  • the reaction temperature was 0- At 5 ° C
  • the aniline was electropolymerized at a current density of 0.04 mA/cm 2 , and the polyaniline on the electrode was scraped off and washed to obtain a polyaniline sample
  • the catalyst slurry was prepared with a 60% Pt/C catalyst, and the Pt of the catalyst slurry was 1 mg.
  • FIG. 25 A cross-sectional electron micrograph of the prepared electrode is shown in Fig. 25. As can be seen from the figure, the capacitance-catalytic composite layer is on the surface of the carbon paper, and the thickness of the composite layer is thicker than that of the conventional electrode.
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested. As shown in Figure 26, the open circuit voltage of this electrode is lower than that of the comparative example.
  • the aniline was chemically polymerized in a 1 mol/L aqueous solution of perchloric acid, the concentration of aniline was 10 mmol/L, the concentration of ammonium persulfate was 6.7 mmol/L, and the reaction was carried out at 0-5 ° C for 24 hours, filtered and dried. Polyaniline sample.
  • the catalyst slurry was prepared with 60% Pt/C catalyst, and the Pt in the catalyst slurry was 1 mg/mL.
  • polyaniline 20% of the total solid mass, polyaniline was added, the concentration of polyaniline was 0.67mg/mL, and the slurry was sprayed onto carbon paper to make the loading of Pt 0.3mg/cm 2 , so that the loading of polyaniline was 0.2 mg/cm 2 .
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested.
  • the aniline was chemically polymerized in a 1 mol/L aqueous solution of perchloric acid, the concentration of aniline was 10 mmol/L, the concentration of ammonium persulfate was 6.7 mmol/L, and the reaction was carried out at 0-5 ° C for 24 hours, filtered and dried. Polyaniline sample.
  • the catalyst slurry was prepared with 60% Pt/C catalyst, and the Pt in the catalyst slurry was 1 mg/mL.
  • the performance of the bifunctional cathode was tested in a 0.5 mol/L sulfuric acid solution with a bifunctional cathode as the working electrode, a Pt plate as the counter electrode, and a saturated calomel electrode as the reference electrode.
  • the open circuit voltage of the dual function cathode in nitrogen and oxygen and the discharge curve in oxygen were tested.
  • the comparative cathode performance was tested in a 0.5 mol/L sulfuric acid solution to compare the cathode as the working electrode, the platinum plate as the counter electrode, and the saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the cathode was tested by passing a high purity nitrogen gas into the solution.
  • the high purity oxygen test was passed into the solution to compare the oxygen reduction reaction polarization curve of the cathode; the constant current discharge curve at 5 mA cm -2 and 40 mA cm -2 current density was tested; the pulse discharge curve was tested and performed every 5 s for 10 ms.
  • the pulse discharge is increased by 20 mA cm -2 for each pulse discharge interval; the test pulse discharge stability is performed every 5 s for 0.5 s pulse discharge, and each pulse discharge current density is 5 mA cm -2 , and the cycle is 500 times.
  • the performance of the comparative anode was tested in a 0.5 mol/L sulfuric acid solution to compare the anode as the working electrode, the platinum plate as the counter electrode, and the saturated calomel electrode as the reference electrode.
  • the cyclic voltammetry curve of the comparative anode was tested by introducing high purity nitrogen into the solution. Methanol was added to the solution to make the methanol concentration 0.5 mol/L.
  • the constant current discharge curve of the comparative anode at a current density of 80 mA cm -2 was tested. The test was compared with the anode pulse discharge curve, and a pulse discharge of 10 ms was performed every 5 s. The pulse discharge interval current is increased by 20 mA cm -2 .
  • the 115 film was an electrolyte membrane, and the comparative cathode in Comparative Example 1 and the comparative anode in Comparative Example 2 were assembled into MEA, and the effective area of the electrode was 1 cm 2 .
  • the battery temperature was 80 ° C
  • the anode 0.5 mol / L methanol aqueous solution was fed
  • the flow rate was 1 mL / min
  • the anode air was fed
  • the flow rate was 80 mL / min.
  • the steady state discharge performance and transient discharge performance of direct methanol fuel cells were tested.
  • the catalyst slurry was configured with a 60% Pt/C catalyst, and the Pt in the catalyst slurry was 1 mg/mL. 20% of the total solid mass, the slurry was sprayed onto a carbon cloth so that the loading of Pt was 0.3 mg/cm 2 .
  • An electron micrograph of the prepared electrode is shown in Fig. 20. As can be seen from the figure, the catalyst is distributed on the surface of the substrate.
  • the comparative cathode performance was tested in a 0.5 mol/L sulfuric acid solution to compare the cathode as the working electrode, the Pt sheet as the counter electrode, and the saturated calomel electrode as the reference electrode.
  • the test compares the open circuit voltage of the cathode in nitrogen and oxygen with the discharge curve in oxygen.
  • the catalyst slurry was configured with a 60% Pt/C catalyst, and the Pt in the catalyst slurry was 1 mg/mL. 20% of the total solid mass, the slurry was sprayed onto carbon paper so that the loading of Pt was 0.3 mg/cm 2 .
  • the comparative cathode performance was tested in a 0.5 mol/L sulfuric acid solution to compare the cathode as the working electrode, the Pt sheet as the counter electrode, and the saturated calomel electrode as the reference electrode.
  • the test compares the open circuit voltage of the cathode in nitrogen and oxygen with the discharge curve in oxygen.

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Abstract

一种双功能电极，包括基底层（1）和附着于所述基底层（1）的电容-催化复合层；所述电容-催化复合层中含有电容材料、电催化剂和粘结剂；或，包括基底层（1），于所述基底层（1）一侧表面附着有含有电容材料的电容层（2）、另一侧表面附着有含有电催化剂的催化层（3）；或，包括基底层（1）和附着于所述基底层（1）上的含有电容材料的电容层（2）和含有电催化剂的催化层（3），所述电容层（2）设置于所述基底层（1）和所述催化层（3）之间；或，包括基底层（1）和附着于所述基底层（1）上的含有电催化剂的催化层（3）和含有电容材料的电容层（2）；所述催化层（3）设置于所述基底层（1）和所述电容层（2）之间。电极组装的电池在不工作时，活性物质反应生成的电荷储存在电极的电容材料中，在接通电路瞬间时，电荷迅速释放出来，从而可以大电流脉冲放电；电容层（2）的厚度可控，可通过控制电容层（2）的厚度来控制双功能电极储存的电荷量；纯电池工作模式下，电容层（2）可以改善电池的动态稳定性。

Description

双功能电极及其制备方法和应用 技术领域
本发明涉及燃料电池和超级电容器制备领域，具体的说涉及一种能在发生电极反应的同时储存电荷的双功能电极。
本发明还涉及上述双功能电极的制备方法。
背景技术
随着民用的可穿戴电子设备、电动汽车和军用的大功率激光武器等的发展，单一电源难以满足需求，可长时间稳定放电和瞬时大电流放电的复合电源将成为发展趋势。目前应用较多的是电池和超级电容器的外部复合，即通过外部电路的控制，使电池和超级电容器可协同工作以满足要求，但是外部复合增加金属导线和模块界面，从而增加电阻，降低性能，同时会增加装置的重量、体积和价格；而电池和超级电容器内部复合(即单一电极可同时进行电化学反应并储存电荷)不存在这些问题，是目前的研究热点。
专利(CN102576613A)中设计了用于车辆推进的燃料电池/超级电容器/电池电力系统，此系统采用外部复合，电路设计较复杂，增加了装置的重量，降低了装置的性能。文献(International Journal of Hydrogen Energy，2010,35,11254-11260)中向直接甲醇燃料电池的电极中加入二氧化钌，利用二氧化钌的电容性能提高电池的动态稳定性，由于二氧化钌的电导较小，电容层中二氧化钌用量较小，存储的电荷较少，不能达到超级电容器的工作要求，故不能作为双功能电极使用。
发明内容
本发明的目的在于制备一种双功能电极，此种双功能电极可催化电极反应的同时储存电能，需要时把储存的电能短时间释放出来，达到瞬间大电流放电的目的。
为实现上述发明内容，本发明采用以下技术方案来实现：
一种双功能电极，包括基底层和附着于所述基底层的电容-催化复合层；所述电容-催化复合层中含有电容材料、电催化剂和粘结剂；
或，包括基底层，于所述基底层一侧表面附着有含有电容材料的电容层、另一侧表面附着有含有电催化剂的催化层；
或，包括基底层和依次附着于所述基底层上的含有电容材料的电容层和含有电催化剂的催化层；所述电容层设置于所述基底层和所述催化层之间。
即，所述基底层、电容层和催化层存在不同组合方式：(1)电容层和催化层在扩散层两侧；(2)电容层和催化层在基底层同侧，电容层紧靠基底层或催化层紧靠基底层；(3)电容层和催化层均匀混合为一层组成电容-催化复合层附着在基底层上。
所述电容-催化复合层中电催化剂的载量为0.05-5mg/cm2，粘结剂质量占电催化剂和粘结剂总质量的5％-50％，电容材料的载量为0.1-50mg/cm2；
或，所述催化层中电催化剂的载量为0.05-5mg/cm2；所述电容层中电容材料的载量为0.1-50mg/cm2；所述催化层中含有粘结剂，所述粘结剂质量占电催化剂和粘结剂总质量的5％-50％。
所述电容材料为导电聚合物；所述基底层为碳纸或碳布中的一种。
所述导电聚合物为聚苯胺、聚吡咯、聚噻吩、聚芴、聚嵌二萘、聚甘菊环、聚萘、聚咔唑、聚吲哚、聚(3,4-乙烯二氧噻吩)或它们的衍生物或它们之间的共聚物中的 一种或两种以上；
所述粘结剂为PTFE或
Figure PCTCN2016109989-appb-000001
所述双功能电极的制备方法，包括(1)电容材料的制备和(2)电容-催化复合层的制备；所述电容材料的制备为采用电化学方法或化学聚合法制备导电聚合物；
或，包括(1)采用电化学方法于基底材料一侧表面制备电容层，或先采用化学聚合方法制备导电聚合物，再采用刷涂或喷涂或丝网印刷中的一种或两种以上将导电聚合物制备于基底材料一侧表面；和(2)采用刷涂或喷涂或丝网印刷中的一种或两种以上于基底材料的另一侧表面制备催化层；
或，包括(1)采用电化学方法于基底材料一侧表面制备电容层，或先采用化学聚合方法制备导电聚合物，再采用刷涂或喷涂或丝网印刷中的一种或两种以上将导电聚合物制备于基底材料一侧表面；和(2)采用刷涂或喷涂或丝网印刷中的一种或两种以上于步骤(1)所制得的电容层表面制备催化层。
所述电容材料的制备采用电化学方法时，为以添加有掺杂酸、导电聚合物单体溶液的电解质溶液中，以一导电基底为工作电极，铂片为对电极，饱和甘汞电极为参比电极，于所述导电基底表面电化学沉积导电聚合物，再将制得的导电聚合物与所述导电基底剥离，得导电聚合物；所述导电基底组分包括铂、金、铜、银中的一种或两种以上；
所述电容层的制备采用电化学方法时，以添加有掺杂酸的导电聚合物单体溶液的电解质溶液中，以所述基底层为工作电极，铂片为对电极，饱和甘汞电极为参比电极，于所述基底层一侧表面电化学沉积导电聚合物，制备所述电容层；
所述采用化学聚合法制备导电聚合物时，于导电聚合物单体溶液中加入掺杂酸和氧化剂使之发生化学聚合反应制备导电聚合物。
所述电化学方法制备电容材料或电容层过程中，导电聚合物单体溶液中，溶剂为甲醇、乙醇、水、乙二醇、异丙醇中的一种或两种以上的混合溶液，导电聚合物单体的浓度为0.001-2mol/L；所述掺杂酸为盐酸、硫酸、高氯酸、硝酸中的一种或两种以上的混合酸；所述掺杂酸的浓度为0.1-2mol/L；所述电化学沉积过程中反应温度为-5-50℃，沉积电流密度为0.01-20mA/cm2。
电容-催化复合层的制备方法为于溶剂中加入步骤(1)所得导电聚合物，以及电催化剂和粘结剂配制成浆液，采用刷涂、喷涂、丝网印刷中的一种或两种以上于一气体扩散层表面制得电容-催化复合层；
所述催化层的制备具体为于溶剂中加入催化剂和粘结剂；所述溶剂为水、乙醇、乙二醇中的一种或两种以上的混合溶剂，所述催化剂于溶剂中的浓度为0.1-5mg/ml，按比例加入粘结剂，形成催化剂浆液，用喷涂、刷涂或丝网印刷中的一种或两种以上。
所述双功能电极的制备方法，所述导电聚合物为聚苯胺、聚吡咯、聚噻吩、聚芴、聚嵌二萘、聚甘菊环、聚萘、聚咔唑、聚吲哚、聚(3,4-乙烯二氧噻吩)或它们的衍生物或它们之间的共聚物中的一种或两种以上的混合物。
所述化学聚合法制备导电聚合物过程中，所述导电聚合物单体溶液的溶剂为甲醇、乙醇、水、乙二醇、异丙醇中的一种或两种以上的混合溶液，导电聚合物单体的浓度为0.001-2mol/L；所述掺杂酸为盐酸、硫酸、高氯酸、硝酸中的一种或两种以上的混合酸；所述掺杂酸的浓度为0.1-2mol/L；所述化学聚合方法中，溶液中氧化剂与导电聚合物单体的物质的量的比为0.5-2；所述反应温度为-5-50℃，反应时间为12-48小时；所述氧化剂为过硫酸铵，氯化铁，过氧化氢，高锰酸钾中的一种或两种以上的混合物。
所述双功能电极的燃料电池-超级电容器一体化发电单元，包括依次层状叠合的 阳极、电解质膜和阴极，所述阳极和/或阴极为双功能电极；所述电解质膜为质子交换膜或碱性阴离子交换膜；
或所述双功能电极单独作为半电池测试其性能。
所述燃料电池-超级电容器一体化发电单元，所述双功能电极中的催化层与所述电解质膜贴接。
所述催化层由贵金属电催化剂或非贵金属电催化剂混合粘结剂组成。
所述贵金属电催化剂为Pt/C、Pt黑、PtRu/C、PtRu黑、PtCo/C或PtCo黑中的一种或两种以上，贵金属载量为0.05-5mg/cm2。
所述非贵金属电催化剂为掺杂氮的碳催化剂，掺杂铁氮的碳催化剂，锰的氧化物催化剂，钴的氧化物催化剂或银催化剂，催化剂载量为0.5-10mg/cm2。
所述粘结剂为
Figure PCTCN2016109989-appb-000002
或聚四氟乙烯。
所述不同组合的双功能电极制备方法如下，
上述组合方式(1)：
(a)电化学聚合法：在含有掺杂酸、导电聚合物单体溶液的电解质溶液中，以一导电基底为工作电极，铂片为对电极，饱和甘汞电极为参比电极，电解液的溶剂为甲醇、乙醇、水、乙二醇、异丙醇中的一种或两种以上的混合溶液，导电聚合物单体的浓度为0.001-2mol/L；所述掺杂酸为盐酸、硫酸、高氯酸、硝酸中的一种或两种以上的混合酸；所述掺杂酸的浓度为0.1-2mol/L；所述电化学聚合过程中反应温度为-5-50℃，电聚合的电流密度为0.01-20mA/cm2。
(b)化学聚合法：于导电聚合物单体溶液中加入掺杂酸和氧化剂使之发生化学聚合反应制备导电聚合物。所述导电聚合物单体溶液的溶剂为甲醇、乙醇、水、乙二醇、异丙醇中的一种或两种以上的混合溶液，导电聚合物单体的浓度为0.001-2mol/L；所述掺杂酸为盐酸、硫酸、高氯酸、硝酸中的一种或两种以上的混合酸；所述掺杂酸的浓度为0.1-2mol/L；所述化学聚合方法中，溶液中氧化剂与导电聚合物单体的物质的量的比为0.5-2；所述反应温度为-5-50℃，反应时间为12-48小时；所述氧化剂为过硫酸铵，氯化铁，过氧化氢，高锰酸钾中的一种或两种以上的混合物。
(c)将电催化剂和粘结剂配成浆液，溶剂为甲醇、乙醇、水、乙二醇、异丙醇中的一种或两种，电催化剂浓度为0.1-5mg/ml，粘结剂占固体总重量的5％-50％，喷涂或刷涂在基底层上(与电容层相对的一面)。
上述组合方式(2)：
导电聚合物的制备与组合方式(1)中(a)(b)步骤相同，然后将电催化剂浆液喷涂或刷涂在基底层上的电容层表面，或在基底层上的催化层表面制备电容层。
上述组合方式(3)：
以铂、金、铜、银为基底，在其上通过电化学聚合法制备导电聚合物，然后剥离得到导电聚合物粉末，或通过化学聚合法制备导电聚合物，然后与电催化剂混合制备浆液，喷涂或刷涂至扩散层上。
以双功能电极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极，测试双功能电极在0.5mol/L的硫酸或1mol/L的高氯酸中测试其性能。
依次层状叠合的阳极、电解质膜和阴极制备复合电源，所述阳极和/或阴极为双功能电极；所述电解质膜为质子交换膜或碱性阴离子交换膜，(1)电容层和催化层在基底层两侧时，所述催化层与所述电解质膜贴接；(2)电容层和催化层在基底层同侧，电容层紧靠基底层或催化层紧靠基底层，所述催化层或电容层与所述电解质膜贴接；(3)电容层和催化层均匀混合为一层组成电容-催化复合层附着在基底层上，所述电容-催化复合层与所述电解质膜贴接。测试复合电源的稳态放电特性和脉冲放 电特性。
与现有电极相比，本双功能电极具有以下优势：
1、组装的电池在不工作时，可以把活性物质的电荷储存在电极的电容材料中，在通路时，迅速把电荷释放出来，可以大电流脉冲放电；
2、电容层或电容-催化复合层的厚度可控，可通过控制电容层的厚度来控制脉冲电流的大小；
3、电容层可同时具有微孔层的作用，是反应物分配更平衡；
4、导电高分子可增加催化剂之间的连接，降低电子电阻；
5、纯电池工作模式下，电容层可以改善电池的动态稳定性；
6、组装的电池结构简单，不需外部复杂的控制电路。
附图说明
图1不同双功能电极结构示意图；图中1为基底层；2为电容层；3为催化层；
图2实施例1中聚苯胺电镜照片；
图3实施例2中聚苯胺电镜照片；
图4实施例3中聚苯胺电镜照片；
图5实施例4中聚苯胺电镜照片；
图6对比例1中碳布电镜照片；
图7实施例1中双功能阴极和对比例1中对比阴极循环伏安曲线；
图8实施例1中双功能阴极和对比例1中对比阴极氧还原反应极化曲线；
图9实施例1中双功能阴极和对比例1中对比阴极在5mA cm-2电流密度下恒流放电曲线；
图10实施例1中双功能阴极和对比例1中对比阴极在40mA cm-2电流密度下恒流放电曲线；
图11实施例1中双功能阴极和对比例1中对比阴极在880mA cm-2至980mA cm-2电流密度脉冲放电曲线；
图12实施例1中双功能阴极和对比例1中对比阴极脉冲放电稳定性；
图13实施例5、6中双功能阳极和对比例2中对比阳极循环伏安曲线；
图14实施例5、6中双功能阳极和对比例2中对比阳极在80mA cm-2电流密度下恒流放电曲线；
图15实施例5、6中双功能阳极和对比例2中对比阳极在880mA cm-2电流密度脉冲放电曲线；
图16实施例9中复合直接甲醇燃料电池和对比例3中直接甲醇燃料电池的稳态放电性能；
图17实施例9中复合直接甲醇燃料电池和对比例3中直接甲醇燃料电池的脉冲放电性能；
图18实施例9中复合直接甲醇燃料电池和对比例3中直接甲醇燃料电池稳态放电性能和脉冲放电性能比较；
图19实施例13的电镜照片；
图20对比例4的电镜照片；
图21实施例14在不通电流密度下的放电曲线；
图22实施例18制备的双功能阴极电容层电镜照片；
图23实施例17制备的双功能阴极的开路电压；从图中可以看出通氮气时电压较低，通氧气时可以自充电，把电荷储存在电极上，电压随时间升高，然后达到一平衡 值；
图24对比例4、实施例17、18的阴极在25mA/cm2电流密度下的放电曲线，从图中可以看出，实施例17、18制备得到的阴极显示出明显的电容性质；
图25实施例22的电镜照片；
图26对比例5、实施例21、22中电极的开路电压，从图中可以看出，由于聚苯胺的加入，开路电压变小。
具体实施方式
实施例1
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布(2×2cm2)作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，聚合温度为25℃，在0.03mA/cm2的电流密度下电聚合制备聚苯胺，使其载量为50mg/cm2，制备得到的聚苯胺电镜照片如图2所述，从图中可以看出，聚苯胺纳米线围绕着碳布中的碳纤维均匀分布。配制60％Pt/C的催化剂浆液，其中Pt浓度1mg/mL，
Figure PCTCN2016109989-appb-000003
占总固体质量的20％，在聚苯胺上喷催化剂浆液，使Pt的载量为1mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试双功能阴极的循环伏安曲线。溶液中通入高纯氧气测试双功能阴极的氧还原反应极化曲线；测试在5mA cm-2和40mA cm-2电流密度下的恒流放电曲线；测试脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2；测试脉冲放电稳定性，每隔5s进行一次持续0.5s的脉冲放电，每个脉冲放电电流密度为5mA cm-2，循环500次。
实施例2
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布(2×2cm2)作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，聚合温度为25℃，在0.03mA/cm2的电流密度下电聚合制备聚苯胺，使其载量为10mg/cm2，制备得到的聚苯胺电镜照片如图3所述，从图中可以看出，聚苯胺纳米线围绕着碳布中的碳纤维均匀分布。配制60％Pt/C的催化剂浆液，其中Pt浓度1mg/mL，
Figure PCTCN2016109989-appb-000004
占总固体质量的20％，在聚苯胺上喷催化剂浆液，使Pt的载量为1mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试双功能阴极的循环伏安曲线。溶液中通入高纯氧气测试双功能阴极的氧还原反应极化曲线；测试在5mA cm-2和40mA cm-2电流密度下的恒流放电曲线；测试脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2；测试脉冲放电稳定性，每隔5s进行一次持续0.5s的脉冲放电，每个脉冲放电电流密度为5mA cm-2，循环500次。
实施例3
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布(2×2cm2)作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，聚合温度为25℃， 在0.03mA/cm2的电流密度下电聚合制备聚苯胺，使其载量为1mg/cm2，制备得到的聚苯胺电镜照片如图4所述，从图中可以看出，聚苯胺纳米线围绕着碳布中的碳纤维均匀分布。配制60％Pt/C的催化剂浆液，其中Pt浓度1mg/mL，
Figure PCTCN2016109989-appb-000005
占总固体质量的20％，在聚苯胺上喷催化剂浆液，使Pt的载量为1mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试双功能阴极的循环伏安曲线。溶液中通入高纯氧气测试双功能阴极的氧还原反应极化曲线；测试在5mA cm-2和40mA cm-2电流密度下的恒流放电曲线；测试脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2；测试脉冲放电稳定性，每隔5s进行一次持续0.5s的脉冲放电，每个脉冲放电电流密度为5mA cm-2，循环500次。
实施例4
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布(2×2cm2)作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，聚合温度为25℃，在0.03mA/cm2的电流密度下电聚合制备聚苯胺，使其载量为0.1mg/cm2，制备得到的聚苯胺电镜照片如图5所述，从图中可以看出，聚苯胺纳米线围绕着碳布中的碳纤维均匀分布。配制60％Pt/C的催化剂浆液，其中Pt浓度1mg/mL，
Figure PCTCN2016109989-appb-000006
占总固体质量的20％，在聚苯胺上喷催化剂浆液，使Pt的载量为1mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试双功能阴极的循环伏安曲线。溶液中通入高纯氧气测试双功能阴极的氧还原反应极化曲线；测试在5mA cm-2和40mA cm-2电流密度下的恒流放电曲线；测试脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2；测试脉冲放电稳定性，每隔5s进行一次持续0.5s的脉冲放电，每个脉冲放电电流密度为5mA cm-2，循环500次。
实施例5
(1)双功能阳极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布(2×2cm2)作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，聚合温度为25℃，在0.03mA/cm2的电流密度下电聚合制备聚苯胺，使其载量为50mg/cm2；配制75％PtRu/C的催化剂浆液，其中PtRu浓度1mg/mL，
Figure PCTCN2016109989-appb-000007
占总固体质量的15％，在聚苯胺上喷催化剂浆液，使PtRu的载量为2mg/cm2。
(2)双功能阳极的测试：
在0.5mol/L的硫酸溶液中测试双功能阳极性能，以双功能阳极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试双功能阳极的循环伏安曲线。溶液中加入甲醇，使甲醇浓度为0.5mol/L，测试在80mA cm-2电流密度下的恒流放电曲线；测试脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2。
实施例6
(1)双功能阳极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布(2×2 cm2)作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，聚合温度为25℃，在0.03mA/cm2的电流密度下电聚合制备聚苯胺，使其载量为10mg/cm2；配制75％PtRu/C的催化剂浆液，其中PtRu浓度1mg/mL，
Figure PCTCN2016109989-appb-000008
占总固体质量的15％，在聚苯胺上喷催化剂浆液，使PtRu的载量为2mg/cm2。
(2)双功能阳极的测试：
在0.5mol/L的硫酸溶液中测试双功能阳极性能，以双功能阳极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试双功能阳极的循环伏安曲线。溶液中加入甲醇，使甲醇浓度为0.5mol/L，测试在80mA cm-2电流密度下的恒流放电曲线；测试脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2。
实施例7
(1)双功能阳极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布(2×2cm2)作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，聚合温度为25℃，在0.03mA/cm2的电流密度下电聚合制备聚苯胺，使其载量为1mg/cm2；配制75％PtRu/C的催化剂浆液，其中PtRu浓度1mg/mL，
Figure PCTCN2016109989-appb-000009
占总固体质量的15％，在聚苯胺上喷催化剂浆液，使PtRu的载量为2mg/cm2。
(2)双功能阳极的测试：
在0.5mol/L的硫酸溶液中测试双功能阳极性能，以双功能阳极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试双功能阳极的循环伏安曲线。溶液中加入甲醇，使甲醇浓度为0.5mol/L，测试在80mA cm-2电流密度下的恒流放电曲线；测试脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2。
实施例8
(1)双功能阳极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布(2×2cm2)作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，聚合温度为25℃，在0.03mA/cm2的电流密度下电聚合制备聚苯胺，使其载量为0.1mg/cm2；配制75％PtRu/C的催化剂浆液，其中PtRu浓度1mg/mL，
Figure PCTCN2016109989-appb-000010
占总固体质量的15％，在聚苯胺上喷催化剂浆液，使PtRu的载量为2mg/cm2。
(2)双功能阳极的测试：
在0.5mol/L的硫酸溶液中测试双功能阳极性能，以双功能阳极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试双功能阳极的循环伏安曲线。溶液中加入甲醇，使甲醇浓度为0.5mol/L，测试在80mA cm-2电流密度下的恒流放电曲线；测试脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2。
实施例9
(1)复合直接甲醇燃料电池的制备：
以
Figure PCTCN2016109989-appb-000011
115膜为电解质膜，把实施例1中双功能阴极和实施例5中双功能阳极组装为复合MEA，电极有效面积为1cm2。
(2)复合直接甲醇燃料电池的测试：
电池温度为80℃，阳极0.5mol/L甲醇水溶液进料，流速为1mL/min，阳极空气进料，流速为80mL/min。测试复合直接甲醇燃料电池稳态放电性能和暂态放电性能。
实施例10
(1)复合直接甲醇燃料电池的制备：
以
Figure PCTCN2016109989-appb-000012
115膜为电解质膜，把实施例2中双功能阴极和实施例6中双功能阳极组装为复合MEA，电极有效面积为1cm2。
(2)复合直接甲醇燃料电池的测试：
电池温度为80℃，阳极0.5mol/L甲醇水溶液进料，流速为1mL/min，阳极空气进料，流速为80mL/min。测试复合直接甲醇燃料电池稳态放电性能和暂态放电性能。
实施例11
(1)复合直接甲醇燃料电池的制备：
以
Figure PCTCN2016109989-appb-000013
115膜为电解质膜，把实施例3中双功能阴极和实施例7中双功能阳极组装为复合MEA，电极有效面积为1cm2。
(2)复合直接甲醇燃料电池的测试：
电池温度为80℃，阳极0.5mol/L甲醇水溶液进料，流速为1mL/min，阳极空气进料，流速为80mL/min。测试复合直接甲醇燃料电池稳态放电性能和暂态放电性能。
实施例12
(1)复合直接甲醇燃料电池的制备：
以
Figure PCTCN2016109989-appb-000014
115膜为电解质膜，把实施例4中双功能阴极和实施例8中双功能阳极组装为复合MEA，电极有效面积为1cm2。
(2)复合直接甲醇燃料电池的测试：
电池温度为80℃，阳极0.5mol/L甲醇水溶液进料，流速为1mL/min，阳极空气进料，流速为80mL/min。测试复合直接甲醇燃料电池稳态放电性能和暂态放电性能。
实施例13
(1)双功能阴极的制备：
取一块2×2cm2的碳布，在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布为基底，把碳布一侧密封，另一侧暴露在溶液中作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，反应温度为0-5℃，在0.04mA/cm2的电流密度下电聚合苯胺，碳布上的聚苯胺的载量为0.2mg/cm2，再在聚苯胺上喷60％Pt/C催化剂，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000015
占总固体质量的20％，碳布上Pt的载量为0.3mg/cm2。制备得到的电极的电镜照片如图19所述，从图中可以看出，催化剂在电容层聚苯胺表面均匀分布。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。
实施例14
(1)双功能阴极的制备：
取一块2×2cm2的碳布，在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布为基底，把碳布一侧密封，另一侧暴露在溶液中作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，反应温度为0-5℃，在0.04mA/cm2的电流密度下电聚合苯胺，碳布上的聚苯胺的载量为2mg/cm2，再在聚苯胺上喷60％Pt/C催化剂，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000016
占总固体质量的20％，碳布上Pt的载量为0.3mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压 和在氧气中的放电曲线。
实施例15
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中化学法聚合苯胺，苯胺的浓度为10mmol/L，过硫酸铵的浓度为6.7mmol/L，在0-5℃温度下反应24小时，过滤洗涤干燥，得聚苯胺样品，配制聚苯胺浆液，聚苯胺的浓度为0.67mg/mL，把浆液喷到碳布一侧上，使聚苯胺的载量为0.2mg/cm2；以60％Pt/C催化剂配制催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000017
占总固体质量的20％，把浆液喷到聚苯胺层上，使Pt的载量为0.3mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。
实施例16
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中化学法聚合苯胺，苯胺的浓度为10mmol/L，过硫酸铵的浓度为6.7mmol/L，在0-5℃温度下反应24小时，过滤洗涤干燥，得聚苯胺样品，配制聚苯胺浆液，聚苯胺的浓度为0.67mg/mL，把浆液喷到碳布一侧上，使聚苯胺的载量为2mg/cm2；以60％Pt/C催化剂配制催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000018
占总固体质量的20％，把浆液喷到聚苯胺层上，使Pt的载量为0.3mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。
实施例17
(1)双功能阴极的制备：
取一块2×2cm2的碳布，在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布为基底，把碳布一侧密封，另一侧暴露在溶液中作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，反应温度为0-5℃，在0.04mA/cm2的电流密度下电聚合苯胺，碳布上的聚苯胺的载量为0.2mg/cm2，再在碳布的另一侧上喷60％Pt/C催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000019
占总固体质量的20％，碳布上Pt的载量为0.3mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。在氮气和氧气中开路电压如图23所示，可看出通氮气时电压较低，通氧气时可以自充电，把电荷储存在电极上，电压随时间升高，然后达到一平衡值。如图24所示，在25mA/cm2电流密度下放电时，电压衰减比对比例1的对比阴极要慢。
实施例18
(1)双功能阴极的制备：
取一块2×2cm2的碳布，在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以碳布为基底，把碳布一侧密封，另一侧暴露在溶液中作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，反应温度为0-5℃，在0.04mA/cm2的电流密度下电聚合苯胺，碳布上的聚苯胺的载量为2mg/cm2，再在碳布的另一侧上喷60％Pt/C 催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000020
占总固体质量的20％，碳布上Pt的载量为0.3mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。电容层的电镜照片及电极的性能分别如图22和图24所示，在25mA/cm2电流密度下的放电时，电压衰减比对比例1的对比阴极要慢，表现出较好的电容效应。
实施例19
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中化学法聚合苯胺，苯胺的浓度为10mmol/L，过硫酸铵的浓度为6.7mmol/L，在0-5℃温度下反应24小时，过滤洗涤干燥，得聚苯胺样品，配制聚苯胺浆液，聚苯胺的浓度为0.67mg/mL，把浆液喷到碳布一侧表面上，使聚苯胺的载量为0.2mg/cm2；以60％Pt/C催化剂配制催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000021
占总固体质量的20％，把浆液喷到碳布另一侧表面上，使Pt的载量为0.3mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。
实施例20
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中化学法聚合苯胺，苯胺的浓度为10mmol/L，过硫酸铵的浓度为6.7mmol/L，在0-5℃温度下反应24小时，过滤洗涤干燥，得聚苯胺样品，配制聚苯胺浆液，聚苯胺的浓度为0.67mg/mL，把浆液喷到碳布一侧表面上，使聚苯胺的载量为2mg/cm2；以60％Pt/C催化剂配制催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000022
占总固体质量的20％，把浆液喷到碳布另一侧表面上，使Pt的载量为0.3mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。
实施例21
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以导电基底作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，反应温度为0-5℃，在0.04mA/cm2的电流密度下电聚合苯胺，把电极上的聚苯胺刮下洗涤干燥，得聚苯胺样品；以60％Pt/C催化剂配制催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000023
占总固体质量的20％，再加入聚苯胺，形成混合浆液，聚苯胺的浓度为0.67mg/mL，把浆液喷到碳纸上，使Pt的载量为0.3mg/cm2，聚苯胺的载量为0.2mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。如图26所示，此电极的开路电压较对比例中电极低。
实施例22
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中加入苯胺，使苯胺的浓度为0.5mol/L，以导电基底作为工作电极，铂片为对电极，饱和甘汞电极为参比电极，反应温度为0-5℃，在0.04mA/cm2的电流密度下电聚合苯胺，把电极上的聚苯胺刮下洗涤干燥，得聚苯胺样品；以60％Pt/C催化剂配制催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000024
占总固体质量的20％，再加入聚苯胺，形成混合浆液，聚苯胺的浓度为6.7mg/mL，把浆液喷到碳纸上，使Pt的载量为0.3mg/cm2，聚苯胺的载量为2mg/cm2。制备得到的电极截面电镜照片如图25所示。从图中够可以看出，电容-催化复合层在碳纸表面，复合层厚度比常规电极要厚。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。如图26所示，此电极的开路电压较对比例中电极低。
实施例23
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中化学法聚合苯胺，苯胺的浓度为10mmol/L，过硫酸铵的浓度为6.7mmol/L，在0-5℃温度下反应24小时，过滤洗涤干燥，得聚苯胺样品。以60％Pt/C催化剂配制催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000025
占总固体质量的20％，再加入聚苯胺，聚苯胺的浓度为0.67mg/mL，把浆液喷到碳纸上，使Pt的载量为0.3mg/cm2，使聚苯胺的载量为0.2mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。
实施例24
(1)双功能阴极的制备：
在1mol/L的高氯酸水溶液中化学法聚合苯胺，苯胺的浓度为10mmol/L，过硫酸铵的浓度为6.7mmol/L，在0-5℃温度下反应24小时，过滤洗涤干燥，得聚苯胺样品。以60％Pt/C催化剂配制催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000026
占总固体质量的20％，再加入聚苯胺，聚苯胺的浓度为6.7mg/mL，把浆液喷到碳纸上，使Pt的载量为0.3mg/cm2，使聚苯胺的载量为2mg/cm2。
(2)双功能阴极的测试：
在0.5mol/L的硫酸溶液中测试双功能阴极性能，以双功能阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试双功能阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。
对比例1
(1)对比阴极的制备：
配制60％Pt/C的催化剂浆液，其中Pt浓度1mg/mL，
Figure PCTCN2016109989-appb-000027
占总固体质量的20％，在碳布上喷催化剂浆液，使Pt的载量为1mg/cm2。
(2)对比阴极的测试：
在0.5mol/L的硫酸溶液中测试对比阴极性能，以对比阴极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试对比阴极的循环伏安曲线。溶液中通入高纯氧气测试对比阴极的氧还原反应极化曲线；测试在5mA cm-2和40mA  cm-2电流密度下的恒流放电曲线；测试脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2；测试脉冲放电稳定性，每隔5s进行一次持续0.5s的脉冲放电，每个脉冲放电电流密度为5mA cm-2，循环500次。
对比例2
(1)对比阳极的制备：
配制75％PtRu/C的催化剂浆液，其中PtRu浓度1mg/mL，
Figure PCTCN2016109989-appb-000028
占总固体质量的15％，在碳布上喷催化剂浆液，使PtRu的载量为2mg/cm2。
(2)对比阳极的测试：
在0.5mol/L的硫酸溶液中测试对比阳极性能，以对比阳极为工作电极，铂片为对电极，饱和甘汞电极为参比电极。溶液中通入高纯氮气测试对比阳极的循环伏安曲线。溶液中加入甲醇，使甲醇浓度为0.5mol/L，测试对比阳极在80mA cm-2电流密度下的恒流放电曲线；测试对比阳极脉冲放电曲线，每隔5s进行一次持续10ms的脉冲放电，每个脉冲放电间隔电流增加20mA cm-2。
对比例3
(1)直接甲醇燃料电池的制备：
以
Figure PCTCN2016109989-appb-000029
115膜为电解质膜，把对比例1中对比阴极和对比例2中对比阳极组装为MEA，电极有效面积为1cm2。
(2)直接甲醇燃料电池的测试：
电池温度为80℃，阳极0.5mol/L甲醇水溶液进料，流速为1mL/min，阳极空气进料，流速为80mL/min。测试直接甲醇燃料电池稳态放电性能和暂态放电性能。
对比例4
(1)对比阴极的制备：
以60％Pt/C催化剂配置催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000030
占总固体质量的20％，把浆液喷到碳布上，使Pt的载量为0.3mg/cm2。制备得到的电极的电镜照片如图20所述，从图中可以看出，催化剂分布在基底表面。
(2)对比阴极的测试：
在0.5mol/L的硫酸溶液中测试对比阴极性能，以对比阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试对比阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。
对比例5
(1)对比阴极的制备：
以60％Pt/C催化剂配置催化剂浆液，催化剂浆液中Pt为1mg/mL，
Figure PCTCN2016109989-appb-000031
占总固体质量的20％，把浆液喷到碳纸上，使Pt的载量为0.3mg/cm2。
(2)对比阴极的测试：
在0.5mol/L的硫酸溶液中测试对比阴极性能，以对比阴极为工作电极，Pt片为对电极，饱和甘汞电极为参比电极。测试对比阴极在氮气和氧气中的开路电压和在氧气中的放电曲线。

Claims (12)

  1. 一种双功能电极，其特征在于：
    包括基底层和附着于所述基底层的电容-催化复合层；所述电容-催化复合层中含有电容材料、电催化剂和粘结剂；
    或，包括基底层，于所述基底层一侧表面附着有含有电容材料的电容层、另一侧表面附着有含有电催化剂的催化层；
    或，包括基底层和依次附着于所述基底层上的含有电容材料的电容层和含有电催化剂的催化层；所述电容层设置于所述基底层和所述催化层之间。
  2. 如权利要求1所述双功能电极，其特征在于：
    所述电容-催化复合层中电催化剂的载量为0.05-5mg/cm2，粘结剂质量占电催化剂和粘结剂总质量的5％-50％，电容材料的载量为0.1-50mg/cm2；
    或，所述催化层中电催化剂的载量为0.05-5mg/cm2；所述电容层中电容材料的载量为0.1-50mg/cm2；所述催化层中含有粘结剂，所述粘结剂质量占电催化剂和粘结剂总质量的5％-50％。
  3. 如权利要求1-2任一所述双功能电极，其特征在于：所述电容材料为导电聚合物；所述基底层为碳纸或碳布中的一种。
  4. 如权利要求3所述双功能电极，其特征在于：所述导电聚合物为聚苯胺、聚吡咯、聚噻吩、聚芴、聚嵌二萘、聚甘菊环、聚萘、聚咔唑、聚吲哚、聚(3,4-乙烯二氧噻吩)或它们的衍生物或它们之间的共聚物中的一种或两种以上；
    所述粘结剂为PTFE或
    Figure PCTCN2016109989-appb-100001
  5. 一种权利要求1-4任一所述双功能电极的制备方法，其特征在于：
    包括(1)电容材料的制备和(2)电容-催化复合层的制备；所述电容材料的制备为采用电化学方法或化学聚合法制备导电聚合物；
    或，包括(1)采用电化学方法于基底材料一侧表面制备电容层，或先采用化学聚合方法制备导电聚合物，再采用刷涂或喷涂或丝网印刷中的一种或两种以上将导电聚合物制备于基底材料一侧表面；和(2)采用刷涂或喷涂或丝网印刷中的一种或两种以上于基底材料的另一侧表面制备催化层；
    或，包括(1)采用电化学方法于基底材料一侧表面制备电容层，或先采用化学聚合方法制备导电聚合物，再采用刷涂或喷涂或丝网印刷中的一种或两种以上将导电聚合物制备于基底材料一侧表面；和(2)采用刷涂或喷涂或丝网印刷中的一种或两种以上于步骤(1)所制得的电容层表面制备催化层。
  6. 如权利要求5所述双功能电极的制备方法，其特征在于：
    所述电容材料的制备采用电化学方法时，为以添加有掺杂酸、导电聚合物单体溶液的电解质溶液中，以一导电基底为工作电极，铂片为对电极，饱和甘汞电极为参比电极，于所述导电基底表面电化学沉积导电聚合物，再将制得的导电聚合物与所述导电基底剥离，得导电聚合物；所述导电基底组分包括铂、金、铜、银中的一种或两种以上；
    所述电容层的制备采用电化学方法时，以添加有掺杂酸的导电聚合物单体溶液的电解质溶液中，以所述基底层为工作电极，铂片为对电极，饱和甘汞电极为参比电极，于所述基底层一侧表面电化学沉积导电聚合物，制备所述电容层；
    所述采用化学聚合法制备导电聚合物时，于导电聚合物单体溶液中加入掺杂酸和氧化剂使之发生化学聚合反应制备导电聚合物。
  7. 如权利要求6所述双功能电极的制备方法，其特征在于：
    所述电化学方法制备电容材料或电容层过程中，导电聚合物单体溶液中，溶剂为甲醇、乙醇、水、乙二醇、异丙醇中的一种或两种以上的混合溶液，导电聚合物单体的浓度为0.001-2mol/L；所述掺杂酸为盐酸、硫酸、高氯酸、硝酸中的一种或两种以上的混合酸；所述掺杂酸的浓度为0.1-2mol/L；所述电化学沉积过程中反应温度为-5-50℃，沉积电流密度为0.01-20mA/cm2。
  8. 如权利要求5所述双功能电极的制备方法，其特征在于：电容-催化复合层的制备方法为于溶剂中加入步骤(1)所得导电聚合物，以及电催化剂和粘结剂配制成浆液，采用刷涂、喷涂、丝网印刷中的一种或两种以上于一气体扩散层表面制得电容-催化复合层；
    所述催化层的制备具体为于溶剂中加入催化剂和粘结剂；所述溶剂为水、乙醇、乙二醇中的一种或两种以上的混合溶剂，所述催化剂于溶剂中的浓度为0.1-5mg/ml，按比例加入粘结剂，形成催化剂浆液，用喷涂、刷涂或丝网印刷中的一种或两种以上。
  9. 如权利要求5-8任一所述双功能电极的制备方法，其特征在于：所述导电聚合物为聚苯胺、聚吡咯、聚噻吩、聚芴、聚嵌二萘、聚甘菊环、聚萘、聚咔唑、聚吲哚、聚(3,4-乙烯二氧噻吩)或它们的衍生物或它们之间的共聚物中的一种或两种以上的混合物。
  10. 如权利要求6所述双功能电极的制备方法，其特征在于：
    所述化学聚合法制备导电聚合物过程中，所述导电聚合物单体溶液的溶剂为甲醇、乙醇、水、乙二醇、异丙醇中的一种或两种以上的混合溶液，导电聚合物单体的浓度为0.001-2mol/L；所述掺杂酸为盐酸、硫酸、高氯酸、硝酸中的一种或两种以上的混合酸；所述掺杂酸的浓度为0.1-2mol/L；所述化学聚合方法中，溶液中氧化剂与导电聚合物单体的物质的量的比为0.5-2；所述反应温度为-5-50℃，反应时间为12-48小时；所述氧化剂为过硫酸铵，氯化铁，过氧化氢，高锰酸钾中的一种或两种以上的混合物。
  11. 一种采用权利要求1-4任一所述双功能电极的燃料电池-超级电容器一体化发电单元，其特征在于：包括依次层状叠合的阳极、电解质膜和阴极，所述阳极和/或阴极为双功能电极；所述电解质膜为质子交换膜或碱性阴离子交换膜；
    或所述双功能电极单独作为半电池测试其性能。
  12. 如权利要求11所述燃料电池-超级电容器一体化发电单元，其特征在于：所述双功能电极中的催化层与所述电解质膜贴接。
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