WO2019114575A1 - Fiber-structured electrode material and preparation thereof - Google Patents

Abstract

Dislcosed is a fiber-structured electrode material, wherein the material is made of a nanofiber structure on a micron or submicron scale in diameter, and the fiber structure further comprises a porous structure with a nano-scale pore diameter and a porosity of 20% to 80%. The porous nanofiber is prepared by compounding a conductive material, a metal material and an ionic polymer, wherein the mass content of the conductive material and the metal in the nanofiber is 50%-99.9%, and the mass ratio of the metal material to the conductive material is 0.01-0.99. The composition of the nanofiber-structured electrode material involves an ionic conductor material and an electronic conductor material. Compared with the prior art, the electrode material of the present invention has an ordered, controllable structure, a good mass transfer performance, a high noble metal utilization rate, a high ion transmission efficiency and a strong practicability.

Description

Electrode material with fiber structure and preparation Technical field

The invention relates to a novel fiber structure electrode and a preparation method thereof. Specifically, the fiber structure electrode has a controllable fiber diameter, a fiber component ratio and a porosity can be adjusted, and a porous nanofiber and a preparation method thereof, It can be used in electrodes such as proton exchange membrane fuel cells, direct liquid fuel cells, metal air batteries and supercapacitors, and lithium ion batteries. The invention also relates to a process for the preparation of the above composite materials.

Background technique

Electrode materials with ordered fiber structure have great application potential in the fields of electronics, energy, biomedicine and the like. Conductive materials suitable for use in electrochemical environments in electrodes are typically carbon-based nanomaterials such as carbon nanotubes, graphene, activated carbon, and the like. One of the distinguishing features of such materials is that they generally exhibit a flexible feature, and in the process of forming a porous electrode, the pore structure is mostly composed of particles stacked into a secondary pore structure. In the application fields of fuel cell electrodes, etc., the structure control structure of the pore structure and the controllability of charge and substance conduction are the basic requirements for studying the basic process of the electrode, explaining the electrochemical behavior of the electrode, and improving the performance of the electrode. In the conventional electrode preparation method, the electrode material slurry is formed by cross-linking and stacking electrode layers on various substrates by various coating techniques, and often has uncontrollable porosity, pore size and pore shape, and it is difficult to achieve electrode performance structure. In-depth research, it is also difficult to achieve an improvement in electrode performance.

In view of this, it is one of the keys to the development of porous electrodes to develop a method for electrode preparation in which pore size and porosity are controllable and the preparation process is simple and easy to apply to most electrode materials.

Due to its high energy conversion efficiency, environmental friendliness and easy start-up, fuel cells have received extensive attention from research institutions at home and abroad in recent years. In a fuel cell, the anode is a fuel oxidation reaction and the cathode is an oxygen reduction reaction. Cathodic reduction reactions are complex with respect to oxidation reactions and often involve processes such as electron transfer, proton transfer, and mass transfer. Therefore, the rational design of cathode materials is essential.

Porous nanofibers are a new type of nanostructured materials developed in recent years. Due to their high electrochemical surface area, low density and flexible structure, porous nanofibers have been widely used in catalysis, medicine and sensing. prospect. Due to its advantages of large electrochemical specific surface area and good pore structure, porous nanofibers have become a research hotspot of fuel cell electrodes.

The porous fibers reported in the literature are mostly porous metal fibers, and the conductive material is metal. Since the metal needs to be crosslinked into a network structure in the porous fiber, the porous fiber can be ensured to have a high electrical conductivity, so that the porous fiber has a high metal content, resulting in a high cost for preparing the porous metal fiber. Therefore, the preparation of highly conductive porous fibers is challenging and promising.

In this paper, a conductive material or a conductive material precursor is added to an electrospinning solution, and a nanofiber having a porous structure is prepared by electrospinning and electrochemical methods.

Summary of the invention

The invention will prepare an electrode material of a fiber structure, the fiber structure electrode has a nanofiber structure in a microscopic morphology, and also has a porous topography characteristic, and the electrode material of the structure is prepared by an electrospinning technique. It can be used as a porous electrode for devices such as fuel cells, metal air batteries, and electrochemical sensors. Among the porous nanofibers, the porous nanofiber has the characteristics of large electrochemical surface area, high catalyst utilization rate, small mass transfer resistance, and the like, and can be used in fuel cells, biomedicine, environmental science and the like.

To achieve the above object, the present invention is implemented by the following specific solutions:

An electrode material having a fiber structure, which is a nanofiber structure having a diameter of micrometer or submicron structure, a diameter ranging from 100 to 2000 nm, and a porous structure having a pore size of nanometers in the fiber structure, and a pore size ranging from 1 to 50 nm, the porosity is 20 to 80%; the porous nanofiber is composed of a conductive material, a doped metal material and an ionic polymer, wherein the conductive material and the metal have a mass content of 50-99.9% in the nanofiber, doping The amount ratio of the material of the metal material and the conductive material is from 0.01 to 0.99.

The constituent components of the fiber structure electrode material are an ion conductor material and an electron conductor material, and the ion conductor material comprises a perfluorosulfonic acid polymer, a polybenzimidazole, a polyetheretherketone, and any of the derivative materials of the three. One or more of the electron conductor materials include one or more of platinum, gold, silver, rhodium, palladium or an alloy of two or more of them; wherein no or additional electrocatalysis may be added A material, an electrocatalytic material, and one or more of a carbon-nitrogen material, a transition metal carbon-nitrogen material, and a transition metal oxide.

The template for forming a metal ion reducing agent and a porous structure in the fiber structure electrode material includes one or more of polyacrylic acid, polyethylene oxide, and polyvinylpyrrolidone.

The preparation method of the fiber structure electrode material comprises the following preparation steps, and is shown in FIG.

a, composite spinning solution preparation

One or more of a certain amount of chloroplatinic acid, chloroauric acid, silver nitrate, cerium chloride, chloropalladium acid, or chloroplatinic acid, chloroauric acid, silver nitrate, cerium chloride, chloropalladium acid One or more of them and one of ferric nitrate, nickel nitrate, cobalt nitrate, and copper nitrate in a ratio of 5:1 to 1:5, adding water, dimethylformamide, methanol, In one or more solvents of ethylene glycol or ethanol, the precious metal has a mass concentration of 1 to 10%, and is sufficiently dissolved for use.

A certain amount of graphene, carbon nanotubes, carbon nanofibers, one or a mixture of two or more of XC-72, BP2000 is added to the above solution to have a mass concentration of 1 to 10%, and ultrasonic 1-4h dispersion Evenly, stir for 2 to 48 hours, dissolve well and wait for use.

Adding a certain mass of ion conductor material, including perfluorosulfonic acid polymer, polybenzimidazole, polyetheretherketone, and any derivative materials thereof, to the above solution to have a mass concentration of 0.1 to 5 %, stir for 2 to 48 hours, fully dissolve and wait until use.

One or more of a certain amount of polyacrylic acid, polyethylene oxide, and polyvinylpyrrolidone are added to the above solution to have a mass concentration of 1% to 20%, and stirred at room temperature to 80 ° C. 2 to 48h, fully dissolved and ready for use.

The above composite solution is heated to 80 to 140 ° C under continuous stirring, and the reaction is continued for 2 to 8 hours, so that the metal ions are completely reduced to nanometer-sized nanoparticles, cooled to room temperature, and continuously stirred for 1 to 4 hours. stand-by.

b. Electrospinning preparation of fiber structure electrode materials

The spinning colloid solution prepared in the above step a is placed at the inlet of the spinning injection device at a feed rate of 0.1 to 2 mL/min, the needle is 5 to 20 cm from the receiver, and the receiver material is aluminum foil, silicon wafer, carbon fiber, carbon. One of paper and carbon cloth, the spinning potential is 10 to 30 kV, and the spinning time is 10 to 600 min. A fiber structure electrode material was thus obtained.

The fibrous structure electrode material can be used in a proton exchange membrane fuel cell, or a metal air battery, or a supercapacitor, or a lithium ion battery.

The nanofibers have a loose porous structure; the porous nanofibers have a diameter of 100-1000 nm, a length of 1 μm or more, and a porosity of 20-85%.

The pores on the porous nanofibers have a diameter of 10 to 100 nm; the conductive material and the metal have a mass content of 70 to 95% in the nanofibers.

The conductive material in the porous nanofiber is one or more of graphene, carbon nanotube, carbon nanofiber, XC-72, BP2000; the metal in the porous nanofiber is platinum, gold, silver One or more of ruthenium and rhodium, and the doping metal is one or more of nickel, cobalt, rhodium, and iron.

The ionic polymer is one of Nafion and organic phosphoric acid.

a method for preparing the porous nanofiber, comprising the following steps,

(1) spinning an electrospinning solution containing a solvent, a polymer, a conductive material, a metal precursor and an ionic polymer into a silk by an electrospinning method; and reducing the obtained sample by a reduction technique to obtain a nanometer fiber;

(2) The composite nanofibers of the step (2) are treated by an electrochemical method to obtain porous nanofibers.

In the step (1), one or a mixture of two or more of solvent water, ethanol, and isopropyl alcohol; and the polymer is one or more of polyacrylic acid, polyvinylpyrrolidone, and polyvinyl alcohol. The mixture, the mass concentration of the polymer is 1.5%-10%; the ionic polymer is one of Nafion, organic phosphoric acid; the mass concentration of the ionic polymer is 0.1%-20%; the conductive material is graphene, carbon nanotube One or a mixture of two or more of carbon nanofibers, XC-72, and BP2000; the metal precursor is one or more of platinum, gold, silver, rhodium, and palladium or an acid One or two or more; the doping metal is one or more of nickel, cobalt, rhodium, iron; the conductive material and the metal precursor in the spinning solution have a mass content of 70%-98.4 %, the amount ratio of the metal precursor and the conductive material is from 0.01 to 0.99.

The reduction technique in the step (1) is one or more of chemical reduction, electrochemical reduction, electron beam reduction, and radiation reduction.

The electrochemical method in the step (2) is to treat the composite nanofibers by a potentiostatic method or a cyclic voltammetry at 60-90 ° C; the potential treated by the potentiostatic method is 0.5 V with respect to a standard hydrogen electrode. 0.8V, the processing time is 1000-6000s; the electrochemical scanning range of the cyclic voltammetry treatment is 0-1.2V with respect to the standard hydrogen electrode, and the scanning circle number is 1000-6000 circles.

The electrode is a nanofiber precursor prepared by collecting an electrospinning method by using a gas diffusion layer or an electrolyte membrane as an electrospinning collector substrate, and then obtaining a porous nanofiber by reduction treatment and electrochemical treatment.

The process for preparing nanofibers by the electrospinning method, the electrospinning voltage is a pressure between the roller substrate and the spinning solution, and is 6kV-30kV; the spinning pitch is a distance between the roller substrate and the spinning solution is 10- 20cm;

The porous nanofibers are in the shape of fibers and have a porous structure; the porous fibers are crosslinked in a network form on the gas diffusion layer or the surface of the electrolyte membrane to form a fuel cell electrode; the porous nanofibers have a diameter of 100-1000 nm and a length of 1 μm or more, a porosity of 20-85%; a pore diameter of the porous nanofiber of 10-100 nm, a porosity of 20-85%; a catalyst particle diameter of 2-20 nm, uniformly distributed in the porous nanofiber; The electrode thickness is 1 μm or more.

Compared with the prior art, the present invention has the following advantages:

1. Structure Order Controllable: The fiber diameter and pore density of the fiber structure electrode material prepared by the method of the present invention can be controlled by the preparation process parameters.

2. Good mass transfer performance: The fiber structure electrode material prepared by the method of the invention has better porosity, better pore order and better mass transfer performance.

3. High utilization rate of precious metal: The fiber structure electrode material prepared by the method of the invention can be mostly exposed to the mass transfer passage, thereby having high utilization rate.

4. High ion transport efficiency: The fiber structure electrode material prepared by the method of the invention has an ion transport channel which is orderly controllable, and the one-dimensional structure can greatly enhance the ion transport process.

5. High practicability: Compared with other preparation methods, the electrospinning method of the method has strong controllability, reduces uncontrollable factors caused by other methods, and has strong practicability.

6. The preparation method of the porous nanofiber of the invention has the characteristics of simplicity, easy implementation and large-scale amplification, and has great application prospects in fuel cells, biomedicine and sensing.

DRAWINGS

1 is a schematic view showing the preparation process and structure of the fiber structure electrode material of the present invention;

2 is a scanning electron micrograph of a fiber structure electrode material prepared by the method of the present invention (Example 1); it can be seen that the fiber structure electrode material exhibits a very regular and orderly fiber structure, and the fiber diameter is about 300 nm. ;

Figure 3 is a graph showing the results of electrochemical test of an oxygen structure reduction electrode material prepared by the method of the present invention (Examples 1, 2, Comparative Example 1 and commercial carbon supported platinum catalyst); The oxygen reduction catalytic performance of the fiber structure electrode material prepared by the method of the invention is obviously improved;

4 is an SEM image of the PtCo nanofiber of Comparative Example 2;

5 is an SEM image of Pt/C/Nafion/PAA nanofibers of Comparative Example 3;

6 is an SEM image of the porous nanofiber Pt-PAA-Nafion-Graphene of Example 5.

Detailed ways

The invention is described in detail below by way of examples, but the invention is not limited to the following examples.

Example 1:

a. Preparation of composite spinning solution

A certain amount of chloroplatinic acid is added to the dimethylformamide solvent so that the precious metal has a mass concentration of 5%, and is sufficiently dissolved for use. A certain amount of perfluorosulfonic acid polyion was added to the above solution to have a mass concentration of 0.5% and stirred for 2 hours. A certain amount of polyacrylic acid was added to the above solution to have a mass concentration of 5%, and stirred at room temperature for 2 hours, fully dissolved and then used.

The above composite solution was heated to 120 ° C under continuous stirring, and the reaction was continued for 4 h, cooled to room temperature, and continuously stirred for 1 h for use.

b. Electrospinning preparation of fiber structure electrode material

The spinning colloid solution prepared in the above step a was placed at the inlet of the spinning injection device, the feeding speed was 0.6 mL/min, the needle distance was 10 cm from the receiver, the receiver material was aluminum foil, the spinning potential was 20 kV, and the spinning time was It is 30min. A fiber structure electrode material was thus obtained. It has a diameter ranging from 100 to 200 nm, a porous structure having a pore size ranging from 10 to 20 nm and a porosity of 50%.

Comparative example 1:

a. Spinning solution preparation

A certain amount of chloroplatinic acid is added to the solvent of dimethylformamide so that the precious metal has a mass concentration of 5%, and is sufficiently dissolved and used. A certain amount of polyacrylic acid was added to the above solution to a mass concentration of 5%, and stirred at room temperature for 24 hours, fully dissolved and then used.

b. Electrospinning preparation

The spinning solution prepared in the above step a was placed in a spinning injection apparatus at a feed rate of 0.6 mL/min, a needle distance of 10 cm from the receiver, and a spinning potential of 20 kV. The prepared composite material is ready for use.

Example 2:

a. Preparation of composite spinning solution

A certain amount of chloroplatinic acid is added to the dimethylformamide solvent so that the precious metal has a mass concentration of 6%, and is sufficiently dissolved and used. A certain amount of perfluorosulfonic acid polyion was added to the above solution to have a mass concentration of 0.5% and stirred for 2 hours. A certain amount of polyvinylpyrrolidone was added to the above solution to have a mass concentration of 6%, and stirred at room temperature for 6 hours, fully dissolved and then used.

The above composite solution was heated to 140 ° C under continuous stirring, and the reaction was continued for 4 h, cooled to room temperature, and continuously stirred for 1 h for use.

b. Electrospinning preparation of fiber structure electrode materials

The spinning colloid solution prepared in the above step a was placed at the inlet of the spinning injection device, the feeding speed was 0.6 mL/min, the needle distance was 10 cm from the receiver, the receiver material was aluminum foil, the spinning potential was 20 kV, and the spinning time was It is 30min. A fiber structure electrode material was thus obtained. It has a diameter ranging from 200 to 300 nm, a porous structure having a pore size ranging from 5 to 10 nm and a porosity of 60%.

Example 3:

a. Preparation of composite spinning solution

A certain amount of chloroauric acid and nickel nitrate, according to the ratio of the amount of the substance is 1:1, added to the ethylene glycol solvent, so that the precious metal mass concentration is 10%, fully dissolved and ready for use. A certain amount of polybenzimidazole was added to the above solution to have a mass concentration of 2% and stirred for 4 hours. A certain amount of polyethylene oxide was added to the above solution to have a mass concentration of 8%, and stirred at room temperature for 4 hours, fully dissolved and then used.

The above composite solution was heated to 130 ° C in an oil bath under continuous stirring, and the reaction was continued for 2 hours, cooled to room temperature, and continuously stirred for 2 hours for use.

b. Electrospinning preparation of fiber structure electrode materials

The spinning colloid solution prepared in the above step a was placed at the inlet of the spinning injection device at a feed rate of 1 mL/min, the needle was 5 cm from the receiver, the receiver material was carbon paper, the spinning potential was 30 kV, and the spinning time was It is 100min. A fiber structure electrode material was thus obtained. It has a diameter ranging from 500 to 1000 nm, a porous structure having a pore size ranging from 40 to 70 nm and a porosity of 70%.

Compared with the comparative example, the preparation method of the prepared porous fiber structure electrode is simple and controllable, the conductivity of the ion conductor is obviously improved, the utilization efficiency of the precious metal catalyst is greatly enhanced, and the electrode performance is obviously improved.

Comparative example 2:

PdCo nanofibers were prepared by Drew C. Higgins, Canada; 34.9 mg PVP was dissolved in 0.9 m methanol; 18.75 mg H2PtCl6.6H2O and 8.15 mg Co(CH3COO)2.6H2O were dissolved in 0.1 ml of deionized water; the above solution was mixed and stirred for 1 h; The above mixed solution was electrospun at a voltage of 6 kV, and the spun fiber was placed at 480 ° C to remove PVP, and then treated in a hydrogen atmosphere for 2 h to obtain PtCo nanofibers; the PtCo nanofibers were solid fibers with a diameter of 40 nm.

Comparative example 3:

PW/C/PAA/Nafion was prepared by Zhang WJ of Vanderbilt University, USA; PAA and Nafion and Pt/C were uniformly mixed with mass fraction of 75%:15%:10%, and the spinning solution mass fraction was 13.4% at 7kV. The voltage was electrospun, and the spun fiber was placed under vacuum at 140 ° C for 10 min to obtain a spun fiber electrode; Pt catalyst particles were present on the surface of the spun fiber, the diameter was 400 nm, and the catalyst was 2-3 nm.

Example 4:

1) Preparation of nanofibers

Dissolving 75 mg of PAA in 1 g of high-purity water, evaporating the solution to 1 g at 70 ° C; dispersing 25 mg of graphene oxide in 2 g of a 10% by mass aqueous solution of chloroplatinic acid, evaporating to 0.5 g at 70 ° C, and uniformly mixing with the above solution; The above mixed solution was electrospun at a voltage of 16 kV, 200 r/min, 35 ° C, using a gas diffusion layer as a receiving material; the spun fiber was vacuum dried at 40 ° C for 12 h, then dried at 140 ° C for 2 h; It was treated at 200 ° C for 2 h in the atmosphere.

2) Preparation of porous nanofibers

The above-mentioned spun fiber was placed in a 0.5 M H ₂ SO ₄ aqueous solution at 70 ° C for 3000 CV test, and vacuum-dried to obtain porous nanofibers; the prepared porous nanofibers had a diameter of 500 nm, an average pore diameter of 20 nm, a porosity of 60%, and interlaced into a network. The shape is distributed on the surface of the gas diffusion layer, and the thickness of the electrode is 1 μm or more.

Example 5:

1) Preparation of nanofibers

25 mg of PAA was dissolved in 1 g of high-purity water, and after stirring, 1 g of 5% Nafion solution was added, and the solution was evaporated to 1 g at 70 ° C; 25 mg of graphene oxide was dispersed in 2 g of an aqueous solution of 8% of chloroplatinic acid, and evaporated at 70 ° C until 0.5g, and mixed with the above solution; using the above mixed solution at 16kV voltage, 200r / min, 35 ° C conditions for electrospinning; the above-mentioned spun fiber was vacuum dried at 40 ° C for 12h, then dried at 140 ° C for 2h; Treated in a hydrogen atmosphere for 2 h.

2) Preparation of porous nanofibers

The above-mentioned spun fiber was placed in a 0.5 M H ₂ SO ₄ aqueous solution at 70 ° C for 3000 CV test, and vacuum-dried to obtain porous nanofibers; the prepared porous composite nanofibers having a diameter of 500 nm, an average pore diameter of 20 nm, and a porosity of 70% were interlaced. The mesh is distributed on the surface of the gas diffusion layer, and the thickness of the electrode is 1 μm or more.

Example 6

The difference from the above Example 4 is that the chloroplatinic acid aqueous solution has a mass of 3 g; the porous nanofiber has a diameter of 750 nm, an average pore diameter of 20 nm, and a porosity of 50%, and the interlaced network is distributed on the surface of the gas diffusion layer, and the electrode thickness is 1 μm. the above.

Example 7

The difference from the above Example 5 is that the chloroplatinic acid aqueous solution has a mass of 3 g; the porous nanofiber has a diameter of 770 nm, an average pore diameter of 30 nm, and a porosity of 60%, and the interlaced network is distributed on the surface of the gas diffusion layer, and the electrode thickness is 1 μm. the above.

Example 8

The difference from the above Example 7 is that the graphene oxide mass is 75 mg; the porous nanofiber has a diameter of 650 nm, an average pore diameter of 20 nm, and a porosity of 50%, and the interlaced network is distributed on the surface of the gas diffusion layer, and the electrode thickness is 1 μm or more. .

Example 9

The difference from the above Example 4 is that the nanofibers are placed in a 0.5 ° C H ₂ SO ₄ aqueous solution at 70 ° C for 2000 CV test to obtain porous nanofibers; the porous nanofibers have a diameter of 600 nm, an average pore diameter of 20 nm, a porosity of 50%, and interlacing. The mesh is distributed on the surface of the gas diffusion layer, and the thickness of the electrode is 1 μm or more.

Example 10:

The difference from the above Example 4 is that the nanofibers are placed in a 0.5 M H ₂ SO ₄ aqueous solution at 70 ° C for 1000 CV test to obtain porous nanofibers; the porous nanofibers have a diameter of 600 nm, an average pore diameter of 10 nm, and a porosity of 40%. The mesh is distributed on the surface of the gas diffusion layer, and the thickness of the electrode is 1 μm or more.

Example 11

The difference from the above Example 5 is that the nanofibers are placed in a 0.5 M H ₂ SO ₄ aqueous solution at 70 ° C for 2000 CV test to obtain porous nanofibers; the porous nanofibers have a diameter of 700 nm, an average pore diameter of 30 nm, and a porosity of 60%, and are interlaced. The mesh is distributed on the surface of the gas diffusion layer, and the thickness of the electrode is 1 μm or more.

Example 12

The difference from the above Example 5 is that the nanofibers are placed in a 0.5 M H ₂ SO ₄ aqueous solution at 70 ° C for 1000 CV test to obtain porous nanofibers; the porous nanofibers have a diameter of 700 nm, an average pore diameter of 20 nm, a porosity of 50%, and interlacing. The mesh is distributed on the surface of the gas diffusion layer, and the thickness of the electrode is 1 μm or more.

Claims (16)

An electrode material having a fiber structure, characterized in that it is a nanofiber structure having a diameter of a micron or a submicron structure, and the fiber structure further comprises a porous structure having a pore size of nanometers, and the porosity is 20 to 80%. The electrode material according to claim 1, wherein said nanofiber structure has a diameter ranging from 100 to 2000 nm; and said pore size ranges from 1 to 100 nm. The electrode material according to claim 2, wherein the porous nanofibers have a pore size in the range of preferably 10 to 50 nm. The electrode material according to any one of claims 1 to 3, wherein the fiber structure electrode material composition comprises an ion conductor material and an electron conductor material. The electrode material according to claim 4, wherein the composition of the fiber structure electrode material further comprises an additive which is one of a doped metal material, a conductive material, and a non-precious metal electrocatalytic material. Kind or more than two. The electrode material according to claim 5, wherein the conductive material is a doped or undoped carbon material, and the carbon material is graphene, carbon nanotubes, carbon nanofibers, XC-72, BP2000. One or more of the doping elements are one or more of nitrogen, phosphorus, sulfur, and boron; the non-precious metal electrocatalytic material is a nitrogen-doped amorphous carbon material, a transition metal nitride One or more of transition metal oxides; the doped metal material is one or more of nickel, cobalt, iron, and copper. The electrode material according to claim 5, wherein the electron conductor material and the additive have a mass content of 50 to 99.9% in the fiber structure electrode material, and the amount ratio of the electron conductor material and the additive substance is 0.01 - 0.99. The electrode material according to claim 5, wherein the electron conductor material and the additive are preferably contained in the fiber structure electrode material in an amount of 70 to 95% by mass. The electrode material according to claim 4, wherein the ion conductor material is an ionic polymer; and the ionic polymer is one or more of the following: a perfluorosulfonic acid polymerization. Or one or more of any one of three, or an organic phosphoric acid; the electron conductor material is platinum, gold, silver, rhodium, palladium Or one or more of the alloys of any two or more of them. A method of preparing an electrode material according to any one of claims 1-9, characterized in that it comprises the following preparation steps: a, composite spinning solution preparation: Preparing a mixed solution containing an electron conductor precursor, an ion conductor and a spinning polymer; the precursor of the electron conductor has a mass concentration of 1% to 10%; the ion conductor has a mass concentration of 0.1% to 5%; The mass concentration of the polymer is from 1% to 20%; after the reaction, a composite spinning solution is obtained; b. Electrospinning preparation of fiber structure electrode materials: The composite spinning solution prepared in the above step a was placed at the inlet of the spinning injection device, and the spinning potential was 10 to 30 kV for spinning to obtain a fiber structure electrode material. The method for preparing an electrode material according to claim 10, wherein the obtained fiber structure electrode material sample is subjected to a reduction treatment by a reduction technique to obtain a nanofiber. The method for preparing an electrode material according to claim 10, wherein the precursor of the electron conductor in the step a is a noble metal precursor salt, which is chloroplatinic acid, chloroauric acid, silver nitrate, cerium chloride, chloropalladium. One or more of the acids; The ion conductor material of the step a is a perfluorosulfonic acid polymer, a polybenzimidazole, a polyetheretherketone, and any of the derivative materials of the three, or an organic phosphoric acid; The spinning polymer in the step a is one or more of polyacrylic acid, polyethylene oxide and polyvinylpyrrolidone; The solvent of the mixed solution in step a is one or more of water, dimethylformamide, methanol or ethanol; The reaction temperature in the step a is from 80 ° C to 140 ° C, and the reaction time is from 2 to 8 h. A method of preparing an electrode material according to claim 10 or 12, wherein: The electron conductor precursor in the step a further contains one or more of a conductive material, a doped metal material precursor salt, and a non-precious metal electrocatalyst material as an additive material; the doped metal material precursor salt nitric acid One or more of iron, nickel nitrate, cobalt nitrate, and copper nitrate; the conductive material is a doped or undoped carbon material, and the carbon material is graphene, carbon nanotubes, carbon nanofibers, One or more of XC-72 and BP2000; the doping element is one or more of nitrogen, phosphorus, sulfur and boron; and the non-precious metal electrocatalytic material is nitrogen-doped amorphous carbon material One or more of a transition metal nitride and a transition metal oxide; The ratio of the amount of the precious metal precursor salt to the additive material is from 5:1 to 1:5. A method of preparing an electrode material according to claim 10, wherein: After the reaction in step a, it is cooled to room temperature under continuous stirring; The feed rate of step b is 0.1 to 2 mL/min; the distance of the needle is 5 to 20 cm from the receiver; the material of the receiver is one of aluminum foil, silicon wafer, carbon fiber, carbon paper, carbon cloth; the spinning time is 10 to 600min. A method of preparing an electrode material according to claim 11, wherein: The preparative reduction technique of the porous nanofibers in the step b is one or more of chemical reduction, electrochemical reduction, electron beam reduction, and radiation reduction. The method for preparing an electrode material according to claim 11 or 15, wherein the obtained fiber structure electrode material sample or the nanofiber is treated by an electrochemical method to obtain a porous nanofiber; and the electrochemical method is 60-90. The composite nanofibers are treated by constant potential method or cyclic voltammetry under the condition of °C; the potential treated by the potentiostatic method is 0.5V-0.8V with respect to the standard hydrogen electrode, and the treatment time is 1000-6000 s; The electrochemical scanning range of the Anfa treatment is 0-1.2V with respect to the standard hydrogen electrode, and the number of scanning cycles is 1000-6000 circles.

Images