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WO2020062307A1 - 直接乙醇燃料电池及其制备方法 - Google Patents

直接乙醇燃料电池及其制备方法 Download PDF

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Publication number
WO2020062307A1
WO2020062307A1 PCT/CN2018/109221 CN2018109221W WO2020062307A1 WO 2020062307 A1 WO2020062307 A1 WO 2020062307A1 CN 2018109221 W CN2018109221 W CN 2018109221W WO 2020062307 A1 WO2020062307 A1 WO 2020062307A1
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Prior art keywords
catalyst
anode
cathode
preparation
solution
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PCT/CN2018/109221
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English (en)
French (fr)
Inventor
黄燕
王稼奇
Original Assignee
哈尔滨工业大学（深圳）
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Priority to PCT/CN2018/109221 priority Critical patent/WO2020062307A1/zh
Priority to US16/691,635 priority patent/US11217810B2/en
Publication of WO2020062307A1 publication Critical patent/WO2020062307A1/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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H01M8/1013—Other direct alcohol fuel cells [DAFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • 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 invention relates to the technical field of batteries, and in particular, to a direct ethanol fuel cell and a preparation method thereof.
  • Fuel cell is an energy conversion device that directly converts the chemical energy of fuel into electrical energy.
  • the reaction process is essentially an oxidation-reduction reaction (ORR).
  • the main components of a fuel cell are: anode, cathode, electrolyte, and current collector. In addition to conducting electrons, the anode and cathode also act as catalysts for redox reactions.
  • Electrolytes are divided into two types, acidic and alkaline. Some studies have shown that the oxidation rate of ethanol in alkaline environment is much faster than that in acidic environment.
  • fuel type fuel cells can be divided into hydrogen fuel cells, methane fuel cells, methanol fuel cells, and ethanol fuel cells. Among them, ethanol fuel cells are popular among people because of their portability, non-toxicity, low cost, and easy storage. The application prospect is very broad.
  • An object of the present invention is to provide a flexible direct ethanol fuel cell that can be practically used, and another object of the present invention is to provide a method for preparing the direct ethanol fuel cell.
  • the present invention provides a method for preparing a direct ethanol fuel cell, including the following steps: a synthesis catalyst: mixing silica powder, sucrose, and thiocyanuric acid, preheating to obtain a mixed powder, and then adding Teflon with The mixed powder is mixed, and the mixture of the mixed powder and Teflon is heated to obtain an N, S co-doped carbon catalyst; a synthetic electrolyte: an initiator is used to polymerize sodium acrylate, and the hydrogel product obtained by soaking the polymerization reaction is in a strong alkali In solution; preparing cathode: coating the N, S co-doped carbon catalyst on the collector to obtain the cathode; preparing anode: coating Pt-Ru / C catalyst on the collector to obtain the anode; preparing battery: soaking The hydrogel is sandwiched between the cathode and the anode to obtain a battery.
  • a synthesis catalyst mixing silica powder, sucrose, and thiocyanuric
  • the present invention also provides a direct ethanol fuel cell including a cathode, an anode, and an electrolyte, the electrolyte is sandwiched between the cathode and the anode, and the cathode is coated with an N, S co-doped carbon catalyst
  • the anode is prepared by coating on a collector, the anode is prepared by coating a collector with a Pt-Ru / C catalyst, and the electrolyte is a sodium polyacrylate alkaline hydrogel electrolyte.
  • the direct ethanol fuel cell provided by the present invention uses a N, S co-doped carbon catalyst to make a cathode.
  • This catalyst is not inactivated by the poisoning of ethanol-catalyzed intermediate products (such as CO), has high catalytic activity, low cost, and
  • the synthesized N, S co-doped carbon catalyst can be directly used to make the cathode without subsequent processing, which effectively simplifies the manufacturing process of the battery.
  • Sodium polyacrylate alkaline hydrogel is used as the electrolyte, which has super strong water absorption and water retention capabilities, and is compatible with strong alkali, has excellent ionic conductivity and durability, and effectively avoids electrolytes in the prior art The problem of easy failure in strong alkaline environment.
  • the battery produced by using N, S co-doped carbon catalyst, Pt-Ru / C catalyst and sodium polyacrylate alkaline hydrogel electrolyte not only has excellent flexibility, but also has a high energy density, and only needs to be added dropwise during use. , You can immediately power electronic clocks, smart phones, etc.
  • FIG. 1 is a schematic diagram of synthesizing N, S co-doped carbon catalysts
  • Figure 2a is the TEM characterization result of N, S co-doped carbon catalyst
  • 2b is an electron energy loss spectrum (EELS) spectrum of a doping element in a N, S co-doped carbon catalyst
  • Figure 3a is a comparison of the electrocatalytic performance of N and S co-doped carbon catalysts at 1 mol / L methanol and without methanol;
  • Figure 3b is the polarization curve of N, S co-doped carbon catalyst in alkaline and acidic environments
  • 3c is a CV curve of an N, S co-doped carbon catalyst
  • FIG. 4 is a schematic diagram of a synthetic sodium polyacrylate alkaline hydrogel electrolyte
  • FIG. 5 is a graph showing the change in the ionic conductivity of a sodium polyacrylate hydrogel film in a 100% stretched state with time
  • FIG. 6 is a schematic diagram of manufacturing a cathode and an anode
  • Figure 7a is the result of the carbon cloth's ability to store ethanol
  • Figure 7b is the result of the sponge's ability to store ethanol
  • 8b is an electron energy loss spectrum (EELS) spectrum of each element in the Pt-Ru / C catalyst
  • Figure 9a is a comparison of the electrocatalytic performance of a Pt-Ru / C catalyst under 1 mol / L methanol and without methanol;
  • Figure 9b is the polarization curve of Pt-Ru / C catalyst under alkaline and acidic environments
  • 9c is a CV curve of a Pt-Ru / C catalyst
  • FIG. 10a is a schematic diagram of using the direct ethanol fuel cell prepared in this embodiment.
  • FIG. 10b is a schematic diagram of using a direct ethanol fuel cell prepared in this embodiment to power a smart phone
  • FIG. 12 is a flexibility test of the direct ethanol fuel cell prepared in this embodiment.
  • the silica powder, sucrose and thiocyanuric acid of equal mass are first dispersed in deionized water, and then concentrated sulfuric acid is added for sufficient stirring, and the mixed solution is ultrasonically processed to perform the preheating step.
  • the weight of the concentrated sulfuric acid accounts for 3% to 5% of the sum of the weights of the silica powder, sucrose, and thiocyanuric acid.
  • the preheating step includes heating the mixed liquid to 90 ⁇ 100 ° C until the liquid evaporates to a solid, and then heating the solid to 150 ⁇ 160 ° C to obtain the mixed powder.
  • the step of heating the mixture of the mixed powder and Teflon includes first heating to 500 to 600 ° C. for 1 to 1.5 hours under an inert atmosphere environment, and then heating to 1000 to 1100 ° C. for 3 to 3.5 hours.
  • the heating rate is 5-8 ° C./min, wherein the ratio of the weight of the Teflon to the weight of the silica powder is 10 or more, and the Teflon is in a powder form.
  • the step of synthesizing the sodium acrylate includes: fully stirring the acrylic monomer and deionized water with a mass ratio of 8: 9 ⁇ 10 to obtain an acrylic solution under an ice bath condition, The sodium hydroxide and deionized water are thoroughly mixed to obtain a sodium hydroxide solution, and the sodium hydroxide solution is slowly added to the acrylic acid solution, wherein the mass ratio of the acrylic monomer to the sodium hydroxide is 2: 1 ⁇ 1.5 After complete neutralization, sodium acrylate is obtained.
  • the temperature of the polymerization reaction is 40 ⁇ 3 ° C, and the time of the polymerization reaction is 30-32h.
  • the hydrogel product obtained by the polymerization reaction is first dried at 100 ° C for 1 hour, and then immersed in the strong alkali solution.
  • the strong alkali solution is a 3 ⁇ 5mol / L potassium hydroxide solution.
  • the step of preparing the cathode includes: mixing a Nafion solution with a mass ratio of 1: 1.8 to 2: 7 to 7.2, isopropyl alcohol, and deionized water to obtain a mixed solution, and then co-doping the N, S A carbon catalyst is dispersed in the mixed solution to obtain a first ink, and the first ink is coated on the collector to obtain a cathode.
  • the step of preparing the anode includes: dispersing the Pt-Ru / C catalyst in the mixed solution to obtain a second ink, and coating the second ink on the collector to obtain an anode,
  • the mass ratio of the mass of the Pt-Ru / C catalyst in the second ink to the mass ratio of the N, S co-doped carbon catalyst in the first ink is 1: 2.
  • the collector is a carbon cloth covered with a sponge layer.
  • This embodiment provides a direct ethanol fuel cell and a preparation method thereof.
  • a direct ethanol fuel cell includes a cathode, an anode, and an electrolyte.
  • the electrolyte is sandwiched between the cathode and the anode.
  • the cathode is prepared by coating an N, S co-doped carbon catalyst on a collector.
  • the anode is coated by a Pt-Ru / C catalyst.
  • the electrolyte is sodium polyacrylate alkaline hydrogel electrolyte.
  • a method for preparing a direct ethanol fuel cell includes the following steps:
  • Step 1 Synthesis of N, S co-doped carbon catalyst by in-situ etching
  • FIG. 1 it is a schematic diagram of synthesizing N, S co-doped carbon catalyst.
  • the silica powder, sucrose and thiocyanuric acid are mixed and pre-heated to obtain a mixed powder; then Teflon is added and mixed with the mixed powder, and the mixture of the mixed powder and Teflon is heated to obtain an N, S co-doped carbon catalyst .
  • the masses of the silica powder, sucrose, and thiocyanuric acid are equal, and the silica powder is preferably fumed silica (fumed silica) having a particle diameter of 200 nm.
  • the silica powder, sucrose, and thiocyanuric acid are first dispersed in deionized water, and then concentrated sulfuric acid is added and stirred thoroughly, wherein the weight of the concentrated sulfuric acid accounts for the silica powder, sucrose, and trimerization.
  • the weight of thiocyanic acid is 3%, and the mass fraction of concentrated sulfuric acid is preferably 96% to 97%.
  • a mixed solution is obtained after ultrasonic treatment for about 10 minutes. The mixed liquid is preheated to obtain the mixed powder.
  • the preheating step includes two steps: First, the mixed liquid is first heated to 100 ° C for liquid evaporation until it becomes a solid, and then the solid is heated to At 160 ° C, sucrose was polymerized and thiocyanic acid was crosslinked to obtain a mixed powder.
  • the obtained mixed powder is first pulverized, and then uniformly mixed with an excess of Teflon. After mixing, it is first heated to 600 ° C for 1 hour in an inert atmosphere, and then at 5 ° C / min The heating rate was raised to 1100 ° C for 3 hours and pyrolyzed to obtain N, S co-doped carbon catalyst powder.
  • the Teflon is a powder having a particle size of 5um, and the ratio of the weight of the Teflon to the weight of the fumed silica powder is 10 or more.
  • the silica powder is formed by the reaction between tetrafluoroethylene (from Teflon) and water (from sucrose).
  • HF is directly etched away, that is, silicon dioxide reacts with HF to generate SiF 4 and volatilizes into the air, thereby avoiding any subsequent processing and effectively simplifying the manufacturing process of the battery.
  • S co-doped carbon catalyst can effectively reduce the cost.
  • Figure 2a shows the TEM characterization results of N and S co-doped carbon catalysts with a scale of 10 nm.
  • Figure 2b shows the electron energy loss spectra of doped elements in N and S co-doped carbon catalysts ( EELS) spectrum with a scale of 1um.
  • the layered pores of the amorphous carbon can be easily seen in Figure 2a, and the doped elements N and S are evenly distributed in the porous carbon skeleton from Figure 2b. Due to the porous structure of the carbon and the uniform distribution of the doped elements It is very helpful to improve the activity of the catalyst. From this, it can be seen that the N, S co-doped carbon catalyst prepared by this method has high catalytic activity.
  • FIG. 4 it is a schematic diagram of a synthetic sodium polyacrylate alkaline hydrogel electrolyte.
  • An initiator is used to cause the polymerization reaction of sodium acrylate, and the hydrogel product obtained by soaking the polymerization reaction is in a strong alkaline solution.
  • the step of synthesizing sodium acrylate includes: fully stirring 48 g of acrylic monomer and 54 g of deionized water in an ice bath to obtain an acrylic acid solution, and thoroughly mixing 26.7 g of sodium hydroxide and 18 g of deionized water to obtain hydrogen. Sodium oxide solution, the sodium hydroxide solution is slowly added to the acrylic acid solution, and after complete neutralization, sodium acrylate is obtained.
  • the initiator is preferably 0.78 g of ammonium persulfate (APS).
  • APS ammonium persulfate
  • the polymerization reaction is performed in an oven at a temperature of 40 ⁇ 3 ° C for 30 hours.
  • the product obtained by the polymerization reaction is sodium polyacrylate hydrogel (PANa). It was dried at 100 ° C. for 1 hour, and then immersed in a 5 mol / L potassium hydroxide solution.
  • FIG. 5 it is a graph of the change in the ionic conductivity of a sodium polyacrylate hydrogel film in a 100% stretched state with time. It can be seen from the figure that even under severe 100% stretching conditions, the conductivity of the sodium polyacrylate hydrogel film is basically stable at about 0.24S / cm for a full 25 hours, which is higher than the existing The ionic conductivity of most polymer electrolytes in the technology is two to three orders of magnitude higher, and sodium polyacrylate hydrogel films have also successfully lit LED bulbs. It can be seen that sodium polyacrylate hydrogel has super flexibility, stability, and long-term stable ionic conductivity. In addition, the sodium polyacrylate alkaline hydrogel has super water absorption and water retention capabilities, and is compatible with strong alkali, which can effectively avoid the problem that the electrolyte in the prior art is liable to fail in a strong alkaline environment.
  • the N, S co-doped carbon catalyst (NSDC) prepared in step 1 is coated on a collector to obtain a cathode, where the collector is preferably a breathable carbon cloth, as shown in FIG. 7 a for carbon cloth storage.
  • the results of the ethanol capacity test can be seen from the figure.
  • the carbon cloth can absorb the same quality of ethanol in a short time of 1s, which is more than the absorption of collector electrodes such as CNT paper and metal mesh commonly used in the prior art. The capacity of ethanol is much stronger.
  • the specific coating method uses the following steps: adding 0.1 g of a 5 wt.% Nafion solution to a mixed solution of 0.18 g of isopropanol and 0.72 g of deionized water, and then co-doping 10 mg of N, S
  • the heterocarbon catalyst is dispersed in the prepared mixed solution to obtain a first ink.
  • the dispersion method uses ultrasonic dispersion for 15 minutes, and the first ink is coated on the collector to obtain a cathode.
  • the catalyst load of the coated cathode is 2 mg / cm 2
  • the coating area is 1 cm 2 .
  • the collector is a carbon cloth covered with a sponge layer. As shown in FIG.
  • the sponge is capable of storing ethanol.
  • the sponge can absorb more in the same short time.
  • the mass of ethanol absorbed by ethanol can reach 33 times its own mass within 1 s.
  • the carbon cloth covered with a sponge layer can greatly improve the ability of the collector to absorb ethanol. With the collector in this embodiment, a long-term discharge of the ethanol fuel cell can be guaranteed.
  • a commercially available Pt-Ru / C catalyst was used to coat the collector to obtain an anode.
  • the coating method is similar to the coating method in step 3, and the Pt-Ru / C catalyst is ultrasonically dispersed in the prepared mixed solution to obtain a second ink, and then the second ink is coated.
  • An anode was obtained on the collector, and the coating area was 1 cm 2. The difference was that the mass of the Pt-Ru / C catalyst was 5 mg, so that the catalyst load of the coated anode was 1 mg / cm 2 .
  • Figure 8a shows the TEM characterization results of the Pt-Ru / C catalyst. Its scale is 5 nm, and the diameter of the nanoparticles in the figure is 3 to 7 nm.
  • the element's electron energy loss spectrum (EELS) spectrum has a scale of 500 nm.
  • Pt and Ru are evenly distributed on the carbon support, which makes the Pt-Ru / C catalyst have many active sites.
  • the hydrogel (that is, sodium polyacrylate alkaline hydrogel electrolyte) soaked in step 2 is sandwiched between the cathode prepared in step 3 and the anode prepared in step 4, and then passed through a thin wire
  • a direct ethanol fuel cell (DEFC) is obtained.
  • FIG. 10a it is a schematic diagram of using the direct ethanol fuel cell prepared by this embodiment. Even if ethanol is added dropwise during use, the electronic clock, smart phone, etc. can be immediately powered.
  • FIG. 10b it is a schematic diagram of using a direct ethanol fuel cell prepared by this embodiment to power a smart phone. It can be seen that the direct ethanol fuel cell prepared by this embodiment can be put into large-scale commercial application.
  • a represents an OCV curve.
  • OCV open-circuit voltage
  • b shows the polarization curve and the corresponding power density calculation. It can be seen from the figure that the battery in this embodiment has reached a maximum output power density of 21.48 mW / cm 2 and can be in a wide range of current density. jobs.
  • c represents a discharge curve at each current density of 0.1 to 1 mA / cm 2.
  • the battery of this embodiment can be continuously discharged for 21 h at a current density of 0.1 mA / cm 2 , and only needs 3 mL of ethanol; Even at high current densities of 0.25 mA / cm 2 , 0.5 mA / cm 2 , and 1 mA / cm 2 , continuous discharges of 13.3 h, 9.8 h, and 4.3 h can be achieved, respectively.
  • d represents the rate performance at various current densities of 0.1 to 1 mA / cm 2. It can be seen from this figure that when the current density is increased multiple times, the discharge voltage also remains high and stable. This shows that the The battery can be well adapted to various currents.
  • e indicates the performance comparison between the direct ethanol fuel cell prepared in this embodiment and other high-performance batteries in the prior art. It can be seen from the figure that with PPy // MnO 2 , LiCoO 2 // Li, TiO 2 // Li, LiCoO 2 // Li 4 Ti 5 O 12 , PANI // Li, LiMn 2 O 4 // Li 4 Compared with high-performance batteries such as Mn 5 O 12 , Ni (OH) 2 // Fe, NiCoO // Zn and PPy // Li, the battery produced in this embodiment has better performance, reaching a maximum of 1.41 mWh / cm 2 Area energy density.
  • FIG. 12 it is a flexibility test of the direct ethanol fuel cell prepared by this embodiment.
  • a represents the discharge curve that is continuously bent 0 °, 30 °, 60 ° to 180 °. It can be seen from the figure that the discharge voltage from 0 ° to 180 ° has only decreased by 0.06V as a whole.
  • b indicates the discharge curve after different bending times. It can be seen from the figure that the battery prepared in this embodiment retains more than 68% of the initial voltage even after being bent for 1000 times. These results fully prove that this embodiment The battery has excellent flexibility.
  • C indicates that three flexible DEFC batteries power the electronic clock in series. It can be seen from the figure that even if the three batteries are severely bent, the three batteries can still be connected in series to power the electronic clock.
  • D is a demonstration of the three-in-one DEFC drop-and-use function. In the absence of ethanol, the DEFC is not powered and the electronic clock is not working. Once ethanol is added, the DEFC is powered and the electronic clock is working. Very small amounts of ethanol are sufficient, enabling unprecedented drop-and-use functionality in battery technology.
  • the weight of the concentrated sulfuric acid is 5% of the sum of the weight of the silica powder, sucrose, and thiocyanuric acid;
  • the preheating step includes heating the mixed liquid to 90 ° C until the liquid evaporates to a solid, and then heating the solid to 150 ° C to obtain the mixed powder;
  • the step of heating the mixture of the mixed powder and Teflon includes first heating to 500 ° C. for 1.5 hours under an inert atmosphere, and then heating to 1000 ° C. for 3.5 hours, and the heating rate is 5 ° C./min;
  • the polymerization reaction time is 32 hours.
  • the product of the polymerization reaction is first dried at 100 ° C. for 1 hour, and then immersed in the strong alkali solution, which is a 3 mol / L potassium hydroxide solution;

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Abstract

本发明涉及电池技术领域，公开了一种直接乙醇燃料电池的制备方法，包括以下步骤：合成催化剂：混合二氧化硅粉末、蔗糖和三聚硫氰酸，预热得混合粉末，再加入特氟龙与所述混合粉末混合，加热所述混合粉末与特氟龙的混合物得N,S共掺杂碳催化剂；合成电解质：采用引发剂使丙烯酸钠发生聚合反应，浸泡聚合反应所得水凝胶产物在强碱溶液中；制备阴极：将所述N,S共掺杂碳催化剂涂覆在集电极上得阴极；制备阳极：将Pt-Ru/C催化剂涂覆在集电极上得阳极；制备电池：将浸泡后的所述水凝胶夹在所述阴极和所述阳极之间得电池。本技术方案的电池具有很高的柔性，能力密度高，且具有即滴即用的功能。

Description

直接乙醇燃料电池及其制备方法 技术领域
本发明涉及电池技术领域，尤其涉及一种直接乙醇燃料电池及其制备方法。
 背景技术
燃料电池是一种把燃料所具有的化学能直接转换成电能的能量转化装置，其反应过程本质上是一种氧化还原反应（ORR）。燃料电池的主要构成组件为：阳极、阴极、电解质和集电器。阳极和阴极除传导电子外，也作为氧化还原反应的催化剂。电解质分为酸性和碱性两类，部分研究表明，乙醇在碱性环境中的氧化速率比在酸性环境中的氧化速率快得多。按燃料类型分类，燃料电池可分为氢燃料电池、甲烷燃料电池、甲醇燃料电池和乙醇燃料电池，其中乙醇燃料电池因其便携、无毒、低成本和易储存等特点而深受人们的喜爱，应用前景十分广阔。
 技术问题
到目前为止，仍然没有可实际应用的柔性的直接乙醇燃料电池（DEFC），其主要原因在于，一方面现有的催化剂容易受到乙醇催化氧化中间产物（例如CO）的毒化而失活，另一方面，现有的电解质在强碱性环境中容易失效。
本发明的一个目的在于提供一种柔性的可实际应用的直接乙醇燃料电池，本发明的另一个目的在于提供一种这种直接乙醇燃料电池的制备方法。
 技术解决方案
一方面，本发明提供一种直接乙醇燃料电池的制备方法，包括以下步骤：合成催化剂：混合二氧化硅粉末、蔗糖和三聚硫氰酸，预热得混合粉末，再加入特氟龙与所述混合粉末混合，加热所述混合粉末与特氟龙的混合物得N,S共掺杂碳催化剂；合成电解质：采用引发剂使丙烯酸钠发生聚合反应，浸泡聚合反应所得水凝胶产物在强碱溶液中；制备阴极：将所述N,S共掺杂碳催化剂涂覆在集电极上得阴极；制备阳极：将Pt-Ru/C催化剂涂覆在集电极上得阳极；制备电池：将浸泡后的所述水凝胶夹在所述阴极和所述阳极之间得电池。
另一方面，本发明还提供一种直接乙醇燃料电池，包括阴极、阳极和电解质，所述电解质夹在所述阴极和所述阳极之间，所述阴极由N,S共掺杂碳催化剂涂覆在集电极上制得，所述阳极由Pt-Ru/C催化剂涂覆在集电极上制得，所述电解质为聚丙烯酸钠碱性水凝胶电解质。
 有益效果
本发明提供的直接乙醇燃料电池，采用N,S共掺杂碳催化剂制作阴极，这种催化剂不会被乙醇催化氧化中间产物（例如CO）的毒化而失活，催化活性高，成本低，且合成的N,S共掺杂碳催化剂可以直接用来制作阴极而不用作后续处理，有效简化了电池的制作过程。采用聚丙烯酸钠碱性水凝胶作为电解质，其具有超强吸水、保水能力，且聚丙烯酸钠与强碱兼容，具有优异的离子导电性和耐用性，有效地避免了现有技术中的电解质在强碱性环境中容易失效的问题。通过采用N,S共掺杂碳催化剂、Pt-Ru/C催化剂和聚丙烯酸钠碱性水凝胶电解质制作出来的电池，不仅具有优异的柔性，而且能量密度高，使用时只需要滴加乙醇，即可马上为电子时钟、智能手机等供电。
 附图说明
本发明的进一步的特征将从以下对优选实施例的描述中变得更加清晰明了，所述优选实施例仅通过示例的方式结合附图提供，其中：
图1为合成N,S共掺杂碳催化剂的示意图；
图2a为N,S共掺杂碳催化剂的TEM表征结果；
图2b为N,S共掺杂碳催化剂中掺杂元素的电子能量损失谱（EELS）谱图；
图3a为N,S共掺杂碳催化剂在1mol/L甲醇和无甲醇情况下的电催化性能比较；
图3b为N,S共掺杂碳催化剂在碱性和酸性环境下的极化曲线；
图3c为N,S共掺杂碳催化剂的CV曲线；
图4为合成聚丙烯酸钠碱性水凝胶电解质的示意图；
图5为聚丙烯酸钠水凝胶膜的在100%拉伸状态下的离子电导率随时间的变化图；
图6为制作阴极和阳极的示意图；
图7a为碳布储存乙醇的能力测试结果；
图7b为海绵储存乙醇的能力测试结果；
图8a为Pt-Ru/C催化剂的TEM表征结果；
图8b为Pt-Ru/C催化剂中各元素的电子能量损失谱（EELS）谱图；
图9a为Pt-Ru/C催化剂在1mol/L甲醇和无甲醇情况下的电催化性能比较；
图9b为Pt-Ru/C催化剂在碱性和酸性环境下的极化曲线；
图9c为Pt-Ru/C催化剂的CV曲线；
图10a为本实施例制得的直接乙醇燃料电池的使用示意图；
图10b为使用本实施例制得的直接乙醇燃料电池为智能手机供电的示意图；
图11为本实施例制得的直接乙醇燃料电池的电化学性能测试结果；
图12为本实施例制得的直接乙醇燃料电池的柔性测试。
 本发明的最佳实施方式
优选地，先将质量相等的所述二氧化硅粉末、蔗糖和三聚硫氰酸分散到去离子水中，然后加入浓硫酸充分搅拌，并超声处理得混合液后再进行所述预热步骤，其中所述浓硫酸的重量占所述二氧化硅粉末、蔗糖和三聚硫氰酸的重量和的3%~5%。
优选地，所述预热步骤包括先将所述混合液加热至90~100℃，直至液体蒸发得固体，再加热所述固体至150~160℃得所述混合粉末。
优选地，加热所述混合粉末与特氟龙的混合物的步骤包括在惰性气氛环境下先加热至500~600℃维持1~1.5小时，再升温加热至1000~1100℃维持3~3.5小时，所述升温的速率为5~8℃/min，其中所述特氟龙的重量与所述二氧化硅粉末的重量之比大于等于10，且特氟龙呈粉末状。
优选地，所述丙烯酸钠的合成步骤包括：将质量比为8:9~10的丙烯酸单体和去离子水在冰浴条件下充分搅拌得丙烯酸溶液，将质量比为1.5:1~1.2的氢氧化钠和去离子水充分混合得氢氧化钠溶液，将所述氢氧化钠溶液缓慢加入所述丙烯酸溶液中，其中所述丙烯酸单体与所述氢氧化钠的质量比为2:1~1.5，完全中和后，即得丙烯酸钠。
优选地，所述聚合反应的温度为40±3℃，聚合反应的时间为30~32h，聚合反应所得水凝胶产物先在100℃下干燥1小时，再浸泡在所述强碱溶液中，所述强碱溶液为3~5mol/L的氢氧化钾溶液。
优选地，所述制备阴极的步骤包括：将质量比为1:1.8~2:7~7.2的Nafion溶液、异丙醇和去离子水混合得一混合溶液，然后将所述N,S共掺杂碳催化剂分散在所述混合溶液中得第一油墨，再将所述第一油墨涂覆在所述集电极上得阴极。
优选地，所述制备阳极的步骤包括：将所述Pt-Ru/C催化剂分散在所述混合溶液中得第二油墨，再将所述第二油墨涂覆在所述集电极上得阳极，其中所述第二油墨中的Pt-Ru/C催化剂的质量与所述第一油墨中的N,S共掺杂碳催化剂的质量比为1：2。
优选地，所述集电极为覆盖有海绵层的碳布。
 本发明的实施方式
为了使本发明的目的和优点能够更加清楚明了，以下将结合附图以及实施例，对本发明进行进一步的详细说明。应该清楚的是，此处所描述的具体实施例的作用仅仅用以解释本发明，并不用于限定本发明。
第一实施例
本实施例提供一种直接乙醇燃料电池及其制备方法。
直接乙醇燃料电池包括阴极、阳极和电解质，电解质夹在阴极和阳极之间，阴极由N,S共掺杂碳催化剂涂覆在集电极上制得，阳极由Pt-Ru/C催化剂涂覆在集电极上制得，电解质为聚丙烯酸钠碱性水凝胶电解质。
本实施例中，直接乙醇燃料电池的制备方法，包括以下步骤：
步骤1：采用原位刻蚀方法合成N,S共掺杂碳催化剂
如图1所示，为合成N,S共掺杂碳催化剂的示意图。混合二氧化硅粉末、蔗糖和三聚硫氰酸，预热得混合粉末；再加入特氟龙与所述混合粉末混合，加热混合粉末与特氟龙的混合物得N,S共掺杂碳催化剂。本实施例中，所述二氧化硅粉末、蔗糖和三聚硫氰酸的质量相等，优选二氧化硅粉末为粒径200nm的气相二氧化硅（气相白炭黑）。在本实施例中，先将二氧化硅粉末、蔗糖和三聚硫氰酸分散到去离子水中，然后加入浓硫酸充分搅拌，其中浓硫酸的重量占所述二氧化硅粉末、蔗糖和三聚硫氰酸的重量和的3%，浓硫酸的质量分数优选为96%~97%，然后用超声波超声处理大约10min后得一混合液。再对该混合液进行预热得所述混合粉末，本实施例中，预热步骤包括两步：一，先将该混合液加热至100℃进行液体蒸发，直至变成固体，再加热固体至160℃，使得蔗糖聚合、三聚硫氰酸交联而得混合粉末。本实施例中，先将制得的该混合粉末磨细，再与过量的特氟龙均匀混合，混合后，在惰性气氛环境下先加热至600℃维持1小时，再以5℃/min的升温速率升温至1100℃维持3小时热解而得N,S共掺杂碳催化剂粉末。较佳的，特氟龙为粒径5um的粉末，且特氟龙的重量与气相二氧化硅粉末的重量之比大于等于10。
在加热混合粉末与特氟龙的混合物得N,S共掺杂碳催化剂的热解过程中，二氧化硅粉末通过四氟乙烯（来自特氟龙）和水（来自蔗糖）之间反应生成的HF而被直接刻蚀掉，即二氧化硅与HF反应生成SiF 4而挥发到空气中，由此避免了任何后续的处理，有效简化了电池的制作过程。且采用该方法制备N,S共掺杂碳催化剂可有效降低成本。
如图2a所示，为N,S共掺杂碳催化剂的TEM表征结果，其比例尺为10nm；如图2b所示，为N,S共掺杂碳催化剂中掺杂元素的电子能量损失谱（EELS）谱图，其比例尺为1um。从图2a可以很容易地看到无定形碳的分层孔隙，从图2b可以看出掺杂元素N和S均匀地分布在多孔碳骨架中，由于碳的多孔结构和掺杂元素的均匀分布非常有助于提高催化剂的活性，由此可以看出，采用本方法制得的N,S共掺杂碳催化剂的催化活性高。
如图3a所示，为N,S共掺杂碳催化剂在1mol/L甲醇和无甲醇情况下的电催化性能比较，其中RHE表示可逆氢电极。从图中可见，有甲醇和无甲醇对N,S共掺杂碳催化剂的电催化性能均没有影响，而甲醇又与乙醇的化学性质和物理性质都极为相似，因此，甲醇对N,S共掺杂碳催化剂无影响等于乙醇对N,S共掺杂碳催化剂无影响，由此验证了N,S共掺杂碳催化剂不受乙醇催化氧化中间产物（例如CO）的毒化影响而失活。如图3b所示，为N,S共掺杂碳催化剂在碱性和酸性环境下的极化曲线，如图3c所示，为N,S共掺杂碳催化剂的CV曲线，从图中可见，相比于酸性环境，N,S共掺杂碳催化剂在碱性环境中显示出更高的电催化活性。
步骤2：合成聚丙烯酸钠碱性水凝胶电解质
如图4所示，为合成聚丙烯酸钠碱性水凝胶电解质的示意图。采用引发剂使丙烯酸钠发生聚合反应，浸泡聚合反应所得水凝胶产物在强碱溶液中。本实施例中，所述丙烯酸钠的合成步骤包括：将48g丙烯酸单体和54g去离子水在冰浴条件下充分搅拌得丙烯酸溶液，将26.7g氢氧化钠和18g去离子水充分混合得氢氧化钠溶液，将所述氢氧化钠溶液缓慢加入所述丙烯酸溶液中，完全中和后，即得丙烯酸钠。本实施例中，引发剂优选为0.78g的过硫酸铵（APS），所述聚合反应在温度为40±3℃的烘箱中进行30h，聚合反应所得产物聚丙烯酸钠水凝胶（PANa）先在100℃下干燥1小时，然后再浸泡在5mol/L的氢氧化钾溶液中。
如图5所示，为聚丙烯酸钠水凝胶膜的在100%拉伸状态下的离子电导率随时间的变化图。从图中可以看出，即使是在严苛的100%拉伸条件下，聚丙烯酸钠水凝胶膜的电导率在整整25个小时内都基本稳定在0.24S/cm左右，这比现有技术中的大多数聚合物电解质的离子电导率都高出了两到三个数量级，而且，聚丙烯酸钠水凝胶膜还成功地点亮了LED灯泡。由此可见，聚丙烯酸钠水凝胶具有超强的柔韧性、稳定性以及长时间稳定的离子导电性。而且聚丙烯酸钠碱性水凝胶作具有超强吸水、保水能力，与强碱兼容，可有效避免现有技术中的电解质在强碱性环境中容易失效的问题。
步骤3：制备阴极
如图6所示，将步骤1制得的N,S共掺杂碳催化剂（NSDC）涂覆在集电极上得阴极，其中集电极优选为透气碳布，如图7a所示为碳布储存乙醇的能力测试结果，从该图中可以看出，碳布可在1s的短时间内即吸收与其自身等质量的乙醇，这比现有技术中常用的CNT纸、金属网等集电极的吸收乙醇的能力强得多。本实施例中，涂覆的具体方法采用以下步骤：将0.1g 5wt.%的Nafion溶液加入0.18g的异丙醇和0.72g的去离子水的混合溶液中，然后将10mg的N,S共掺杂碳催化剂分散在制得的混合溶液中得第一油墨，优选的，分散方法采用超声分散15分钟，再将所述第一油墨涂覆在所述集电极上得阴极。本实施例中，涂覆后的阴极的催化剂载量为2mg/cm 2，涂覆面积为1cm 2。本实施例中，所述集电极为覆盖有海绵层的碳布，如图7b所示为海绵储存乙醇的能力测试结果，从图中可以看出，海绵可以在相同的短时间内吸收更多的乙醇，其吸收乙醇的质量可在1s内达到其自身质量的33倍，由此可见，采用覆盖有海绵层的碳布可极大地提高集电极对乙醇的吸收能力。采用本实施例中的集电极，可保证乙醇燃料电池的长时间放电。
步骤4：制备阳极
采用市售的Pt-Ru/C催化剂涂覆在集电极上得阳极。本实施例中，涂覆方式和步骤3中的涂覆方式相似，也是将Pt-Ru/C催化剂采用超声分散在所述制得的混合溶液中得第二油墨，再将第二油墨涂覆在集电极上得阳极，涂覆面积为1cm 2，不同点在于，Pt-Ru/C催化剂的质量为5mg，使得涂覆后的阳极的催化剂载量为1mg/cm 2。
如图8a所示，为Pt-Ru/C催化剂的TEM表征结果，其比例尺为5nm，图中的纳米颗粒的直径为3~7nm；如图8b所示，为Pt-Ru/C催化剂中各元素的电子能量损失谱（EELS）谱图，其比例尺为500nm，从图中可以看出，Pt和Ru均匀地分布在碳载体上，这使得Pt-Ru/C催化剂具有很多活性位点。
如图9a所示，为Pt-Ru/C催化剂在1mol/L甲醇和无甲醇情况下的电催化性能比较，从图中可以看出Pt-Ru/C催化剂具有突出的醇类氧化性能，所以采用Pt-Ru/C催化剂作为本实施例中电池的阳极，可保证在对乙醇的氧化作用。如图9b所示，为Pt-Ru/C催化剂在碱性和酸性环境下的极化曲线，如图9c所示，为Pt-Ru/C催化剂的CV曲线，从图中可见，相比于酸性环境，Pt-Ru/C催化剂在碱性环境中显示出更高的氧化性能。
步骤5：制备电池
将步骤2中浸泡后的所述水凝胶（即聚丙烯酸钠碱性水凝胶电解质）夹在步骤3制得的所述阴极和步骤4制得的所述阳极之间，然后通过细线等将阴极、电解质和阳极组装在一起，即得直接乙醇燃料电池（DEFC）。如图10a所示，为使用采用本实施例制得的直接乙醇燃料电池的示意图，即使用时只需要滴加乙醇，即可马上为电子时钟、智能手机等供电。如图10b所示，为使用采用本实施例制得的直接乙醇燃料电池为智能手机供电的示意图。由此可见，采用本实施例制得的直接乙醇燃料电池可以投入大规模的商业化实际应用。
如图11所示，为采用本实施例制得的直接乙醇燃料电池的电化学性能测试（在室温和大气压下进行）结果，其中a表示OCV曲线，从该图可以看出，本实施例中的电池的开路电压（OCV）达到了最大值1.14V并稳定在0.73V以上，验证了本实施例中的电池可在高电化学动力学中运行。b示出了极化曲线及相应的功率密度计算，从该图可以看出，本实施例中的电池达到了21.48 mW/cm 2的最大输出功率密度且能够在很宽的电流电流密度范围内工作。c表示0.1~1mA/cm 2的各个电流密度下的放电曲线，从该图可以看出，本实施例的电池在0.1mA/cm 2的电流密度下可连续放电21h，且只需要3mL乙醇；即使是在0.25mA/cm 2、0.5mA/cm 2、1mA/cm 2的高电流密度下也可分别连续放电13.3h、9.8h、4.3h。d表示0.1~1mA/cm 2的各个电流密度下的速率性能，从该图可以看出，当电流密度多次增加的时候，放电电压也保持高而稳定的状态，这说明，本实施例的电池可以很好地适应于各种电流。e表示采用本实施例制得的直接乙醇燃料电池与其他现有技术中的高性能电池之间的性能比较。从图中可以看出，与PPy // MnO 2，LiCoO 2 // Li，TiO 2 // Li，LiCoO 2 // Li 4Ti 5O 12，PANI // Li，LiMn 2O 4 // Li 4Mn 5O 12，Ni（OH） 2 // Fe，NiCoO // Zn和PPy // Li 等高性能电池相比，本实施例制得的电池性能更优，达到了1.41 mWh/cm 2的最大面积能量密度。
如图12所示，为采用本实施例制得的直接乙醇燃料电池的柔性测试。其中a表示连续弯曲0°、30°、60°至180°的放电曲线，从图中可以看出从0°到180°放电电压只整体降低了0.06V。b表示经历不同弯曲次数的放电曲线，从图中可以看出本实施例制得的电池即使在弯曲了1000次以后还是保留了超过68%的初始电压，这些结果都充分证明了本实施例的电池具有优异的柔性。C表示三个柔性的DEFC电池串联地为电子钟提供动力，从图中可以看出，即使三个电池都严重弯曲，但是三个电池还是能够串联起来为电子时钟供电。D为三个串联DEFC即滴即用功能的演示，在没有滴加乙醇的情况下，DEFC没有供电，电子时钟没有工作，而一旦滴加乙醇，DEFC即供电，电子时钟即工作，且仅需要非常少量的乙醇即可，实现了电池技术领域前所未有的即滴即用功能。
第二实施例
本实施例与第一实施例相同的部分在此已省略而不再赘述，其不同点在于：
所述浓硫酸的重量占所述二氧化硅粉末、蔗糖和三聚硫氰酸的重量和的5%；
所述预热步骤包括先将所述混合液加热至90℃，直至液体蒸发得固体，再加热所述固体至150℃得所述混合粉末；
加热所述混合粉末与特氟龙的混合物的步骤包括在惰性气氛环境下先加热至500℃维持1.5小时，再升温加热至1000℃维持3.5小时，所述升温的速率为5℃/min；
将48g丙烯酸单体和60g去离子水在冰浴条件下充分搅拌得丙烯酸溶液，将27g氢氧化钠和21g去离子水充分混合得氢氧化钠溶液；
所述聚合反应的时间为32h，聚合反应所得产物先在100℃下干燥1小时，再浸泡在所述强碱溶液中，所述强碱溶液为3mol/L的氢氧化钾溶液；
将0.1g 5wt.%的Nafion溶液、0.2g异丙醇和0.7g去离子水混合得一混合溶液。
以上所述仅为本发明的较佳实施例，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. 直接乙醇燃料电池的制备方法，其特征在于，包括以下步骤：
    合成催化剂：混合二氧化硅粉末、蔗糖和三聚硫氰酸，预热得混合粉末，再加入特氟龙与所述混合粉末混合，加热所述混合粉末与特氟龙的混合物得N,S共掺杂碳催化剂；
    合成电解质：采用引发剂使丙烯酸钠发生聚合反应，浸泡聚合反应所得水凝胶产物在强碱溶液中；
    制备阴极：将所述N,S共掺杂碳催化剂涂覆在集电极上得阴极；
    制备阳极：将Pt-Ru/C催化剂涂覆在集电极上得阳极；
    制备电池：将浸泡后的所述水凝胶夹在所述阴极和所述阳极之间得电池。
  2. 根据权利要求1所述的制备方法，其特征在于，先将质量相等的所述二氧化硅粉末、蔗糖和三聚硫氰酸分散到去离子水中，然后加入浓硫酸充分搅拌，并超声处理得混合液后再进行所述预热步骤，其中所述浓硫酸的重量占所述二氧化硅粉末、蔗糖和三聚硫氰酸的重量和的3%~5%。
  3. 根据权利要求2所述的制备方法，其特征在于，所述预热步骤包括先将所述混合液加热至90~100℃，直至液体蒸发得固体，再加热所述固体至150~160℃得所述混合粉末。
  4. 根据权利要求1至3中任一项所述的制备方法，其特征在于，加热所述混合粉末与特氟龙的混合物的步骤包括在惰性气氛环境下先加热至500~600℃维持1~1.5小时，再升温加热至1000~1100℃维持3~3.5小时，所述升温的速率为5~8℃/min，其中所述特氟龙的重量与所述二氧化硅粉末的重量之比大于等于10，且特氟龙呈粉末状。
  5. 根据权利要求1至3中任一项所述的制备方法，其特征在于，所述丙烯酸钠的合成步骤包括：将质量比为8:9~10的丙烯酸单体和去离子水在冰浴条件下充分搅拌得丙烯酸溶液，将质量比为1.5:1~1.2的氢氧化钠和去离子水充分混合得氢氧化钠溶液，将所述氢氧化钠溶液缓慢加入所述丙烯酸溶液中，其中所述丙烯酸单体与所述氢氧化钠的质量比为2:1~1.5，完全中和后，即得丙烯酸钠。
  6. 根据权利要求5所述的制备方法，其特征在于，所述聚合反应的温度为40±3℃，聚合反应的时间为30~32h，聚合反应所得水凝胶产物先在100℃下干燥1小时，再浸泡在所述强碱溶液中，所述强碱溶液为3~5mol/L的氢氧化钾溶液。
  7. 根据权利要求1至3中任一项所述的制备方法，其特征在于，所述制备阴极的步骤包括：将质量比为1:1.8~2:7~7.2的Nafion溶液、异丙醇和去离子水混合得一混合溶液，然后将所述N,S共掺杂碳催化剂分散在所述混合溶液中得第一油墨，再将所述第一油墨涂覆在所述集电极上得阴极。
  8. 根据权利要求7所述的制备方法，其特征在于，所述制备阳极的步骤包括：将所述Pt-Ru/C催化剂分散在所述混合溶液中得第二油墨，再将所述第二油墨涂覆在所述集电极上得阳极，其中所述第二油墨中的Pt-Ru/C催化剂的质量与所述第一油墨中的N,S共掺杂碳催化剂的质量比为1：2。
  9. 直接乙醇燃料电池，包括阴极、阳极和电解质，所述电解质夹在所述阴极和所述阳极之间，其特征在于，所述阴极由N,S共掺杂碳催化剂涂覆在集电极上制得，所述阳极由Pt-Ru/C催化剂涂覆在集电极上制得，所述电解质为聚丙烯酸钠碱性水凝胶电解质。
  10. 根据权利要求9所述的直接乙醇燃料电池，其特征在于，所述集电极为覆盖有海绵层的碳布。
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