CN110407577B

CN110407577B - Ceramic film material, catalytic electrode, preparation method and application thereof

Info

Publication number: CN110407577B
Application number: CN201910681627.0A
Authority: CN
Inventors: 王田军; 陈彬; 胡延超; 徐斌; 李敏; 苗伟峰
Original assignee: Shenzhen Fuji New Material Technology Co ltd
Current assignee: Shenzhen Fuji New Material Technology Co Ltd
Priority date: 2019-07-26
Filing date: 2019-07-26
Publication date: 2022-05-17
Anticipated expiration: 2039-07-26
Also published as: CN110407577A

Abstract

The invention provides a ceramic film material, a catalytic electrode, a preparation method and application thereof. The catalytic electrode provided by the invention has good stability, catalytic activity and low manufacturing cost. The solid fuel cell of the invention has good stability and energy conversion efficiency due to the adoption of the catalytic electrode.

Description

Ceramic film material, catalytic electrode, preparation method and application thereof

Technical Field

The invention belongs to the field of solid fuel cells, and particularly relates to a catalytic electrode of a solid fuel, and a preparation method and application thereof.

Background

Solid Fuel Cell (SFC) is an all-Solid-state chemical power generation device that directly converts chemical energy stored in Fuel and oxidant into electrical energy at medium and high temperature with high efficiency and environmental friendliness. Its high efficiency, non-pollution, all-solid-state structure and wide adaptability to various fuel gases, etc. are the basis of its wide application.

The main components of the solid fuel cell include an electrolyte (electrolyte), an anode or a fuel electrode (anode), a cathode or an air electrode (cathode), a Catalytic electrode (Catalytic electrode), and a connector (interconnect) or a bipolar plate (bipolar separator).

The working principle of the solid fuel cell is that the anode is a place where fuel is oxidized, and the cathode is a place where oxidant is reduced, and is a catalyst for chemical reaction. When working, the power supply is equivalent to a direct current power supply, the anode of the power supply is the negative pole of the power supply, and the cathode of the power supply is the positive pole of the power supply.

The anode side of the solid fuel cell is continuously fed with fuel gas, such as: hydrogen (H2), methane (CH4), city gas, etc., and the fuel gas is adsorbed on the surface of the anode having a catalytic action and diffuses to the interface between the anode and the electrolyte through the porous structure of the anode. Oxygen or air is continuously introduced to one side of the cathode, oxygen is adsorbed on the surface of the cathode with a porous structure, O2 obtains electrons to become O2-due to the catalytic action of the cathode catalytic electrode, O2-enters a solid oxygen ion conductor which plays the role of an electrolyte under the action of chemical potential, and finally reaches the interface between the solid electrolyte and the anode due to diffusion caused by concentration gradient to react with fuel gas, and the lost electrons return to the cathode through an external circuit.

Fuel gas enters from the anode of the fuel cell and is decomposed into positive ions and electrons through an anode catalyst, then the electrons form current through an external circuit to reach the cathode, and the fuel gas loses the electrons and then passes through an electrolyte to O2 < - > of the cathode of the partition wall; the reaction takes place with the aid of a cathode catalyst to form water.

The above characteristics make hydrogen fuel cells one of the alternative energy sources of fossil fuels, especially the promising power source for electric vehicles, and unfortunately, platinum as a catalyst is expensive, and scarce in raw materials, and thus cannot be used in a large amount for fuel cells. Scientists have attempted to use other metals, alloys or compounds as catalysts, but with less than platinum performance.

Disclosure of Invention

The invention aims to provide a ceramic film material to solve the technical problems that the specific surface area of the existing ceramic film material used as a loading substrate of a catalyst is not large enough, the adsorption capacity is weak, and the catalyst activation capacity is not enough.

The invention also aims to provide a catalytic electrode and a preparation method thereof, which are used for solving the technical problems of high price, insufficient stability and insufficient catalytic activity of the existing catalytic electrode.

The invention also aims to provide a solid fuel cell to solve the technical problems of high cost, insufficient stability and low energy conversion efficiency of the conventional solid fuel cell.

In order to solve the technical problems, the invention provides a ceramic thin film material, which comprises a substrate and a ceramic thin film layer loaded on the substrate, wherein the ceramic thin film layer is prepared by sintering ceramic slurry prepared from 10-20% of organic zirconium compound, 0.3-2.8% of organic hafnium compound, 1.0-4.2% of yttrium and cerium compound, 3-5.5% of nano carbon fiber, 2.5-8.0% of pore-forming agent and 70% of organic solvent by mass.

Preferably, the thickness of the ceramic thin film layer is 0.5-20 um.

Preferably, the organozirconium compound comprises at least one of biscyclopentadienyl or bis (methylcyclopentadienyl) zirconium dichloride, zirconium isooctanoate, zirconium 2-ethylhexanoate, zirconocene dichloride, tetrabenzylzirconium tetrakis (ethylmethylamino) zirconium (IV), zirconium bis [2- (2-benzothiazolyl) phenol ] zinc tetramethylacrylate n-propoxide, zirconium hexafluoro-acetylacetonate, zirconium bis (n-butylcyclopentadienyl) zirconium acetylacetonate, cyclopentadienyl zirconium trichloride, tetrakis (dimethylamino) zirconium, 1.1.1-trifluoroacetylacetonate, zirconium (IV) pentamethylcyclopentadienyl trichloride, zirconium tetrakis (2,2,6, 6-tetramethyl-3, 5-heptanedioate) zirconium.

Preferably, the organohafnide comprises at least one of biscyclopentadienyl or bis (methylcyclopentadienyl) zirconium dichloride, zirconium isooctanoate, zirconium 2-ethylhexanoate, zirconocene dichloride, tetrabenzylzirconium tetrakis (ethylmethylamino) zirconium (IV), hafnium acetylacetonate, hafnium (IV) trifluoromethanesulfonate.

Preferably, the yttrium compound comprises at least one of yttrium (III) isopropoxide, yttrium (III) trifluoromethanesulfonate, yttrium nitrate, yttrium (2,2,6, 6-tetramethyl-3, 5-heptanedionate).

Preferably, the cerium compound includes at least one of cerium (III) carbonate, cerium (III) nitrate, cerium (III) acetate, cerium oxalate, and cerium trifluoromethanesulfonate.

Preferably, the diameter of the nano carbon fiber is 30-400nm, and the length is 2um-500 um;

preferably, the pore-forming agent comprises at least one of nano carbon black, PS micro powder and PMMA micro powder, and the microscopic shape of the pore-forming agent is at least one of dendritic shape, spherical shape and sheet shape; the particle size of the pore-forming agent is 0.05um-10 um.

The invention also provides a catalytic electrode, which comprises the ceramic film material and a catalytic layer coated on the ceramic film layer in the ceramic film material, wherein the catalytic layer is prepared by sintering catalytic slurry prepared from 2.5-18% of organic platinum compound, 3.5-20% of nano carbon black, 4.5-12% of organic adhesive, 0.5-2.0% of dispersing agent and 35-60% of organic solvent by mass.

Preferably, the catalytic layer has a thickness of 0.02um to 0.3 um.

Preferably, the platinum compound includes at least one of a carbonyl complex of platinum, divinyldichloroplatinum, tetraammineplatinum nitrate, dinitrosoplatinum, bis (cyanophenyl) dichloroplatinum (II), tetrachloroplatnum tetraammineplatinate, bis (tri-tert-butylphosphine) platinum (0), platinum (II) acetylacetonate, tetrakis (triphenylphosphine) platinum, cis-dichlorobis (diethylsulfide) platinum (II), 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0).

The shape of the nano carbon black is at least one of dendritic shape, spherical shape and sheet shape; the particle size of the nano carbon black is 80nm-500 nm.

The invention also provides a preparation method of the catalytic electrode, which is characterized by comprising the following steps:

dispersing 10-20% of organic zirconium compound, 0.3-2.8% of organic hafnium compound, 1.0-4.2% of yttrium and cerium compound, 3-5.5% of nano carbon fiber and 2.5-8.0% of pore-forming agent in 70% of organic solvent to prepare ceramic slurry;

coating the slurry on the substrate, and drying and sintering to obtain a ceramic thin film layer loaded on the substrate;

and (2) dispersing 2.5-18% of organic platinum compound, 3.5-20% of nano carbon black, 4.5-12% of organic adhesive and 0.5-2.0% of dispersant in 70% of organic solvent to prepare catalytic slurry, loading the catalytic slurry on the ceramic film layer, and drying, calcining and sintering to obtain the catalytic electrode.

Preferably, the sintering treatment of the ceramic thin film layer is a laser activated sintering treatment.

Preferably, the catalytic slurry is supported by a dip coating method.

Preferably, the sintering mode of the catalytic slurry is microwave sintering.

In yet another aspect, the present invention provides a solid fuel cell comprising the catalytic electrode.

Compared with the prior art, on one hand, the ceramic film material provided by the invention adopts rare earth elements to dope the zirconia with the auxiliary catalytic function, so that the conductivity, thermal stability and catalytic activity of the zirconia are improved; on the other hand, the carbon nano-fiber and the pore-forming agent are decomposed at high temperature to form a communicated pore network structure, so that the porosity and the specific surface area are improved, and the circulation and the exchange of gas are facilitated; on the other hand, the surface of the ceramic is sintered and activated by laser, so that the doping of the rare earth elements in the ceramic to the zirconia material is promoted, and the surface of the activated ceramic particles is favorable for being combined with a subsequent catalytic layer. Generally, the conductivity, stability and auxiliary catalytic capability of the ceramic material as a catalytic load material are improved.

On one hand, the catalytic electrode is based on the ceramic film material, so that the catalytic electrode has the advantages of large specific surface area, good stability and electrical conductivity and good catalytic activity. On the other hand, a layer of catalyst layer is paved on the surface by dip coating, then the superfine platinum particles are combined with the surface of the ceramic by rapid sintering, the crystal grains of the platinum particles are refined, the surface activity of the nascent platinum is maintained, and the catalytic activity is further improved. Finally, because a large amount of auxiliary catalytic materials are used, and the process is improved, the consumption of noble metal platinum is greatly reduced, and the cost is greatly reduced.

The preparation method of the catalytic electrode has high efficiency and low cost, and the prepared catalytic electrode has excellent functions.

The solid fuel cell of the invention has good stability and energy conversion efficiency due to the adoption of the catalytic electrode.

Drawings

Fig. 1 is a scanning electron microscope image of a catalytic electrode according to an embodiment of the invention.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The ceramic film layer is prepared by sintering ceramic slurry which is prepared from 10-20% of organic zirconium compound, 0.3-2.8% of organic hafnium compound, 1.0-4.2% of yttrium and cerium compound, 3-5.5% of nano carbon fiber, 2.5-8.0% of pore forming agent and 70% of organic solvent by mass.

Specifically, the substrate is made of conventional ceramic or glass materials, organic zirconium compounds are used as raw materials, zirconium oxide is formed by sintering, certain catalytic capacity is achieved, and meanwhile rare earth metal oxides such as hafnium, yttrium and cerium are doped, so that the ionic conductivity, the thermal stability and the catalytic activity of zirconium oxide powder particles are improved. More specifically, in a preferred embodiment the ceramic membrane layer has a thickness of 0.5-20 um. The ceramic thin film layer is formed on the substrate using the slurry in the preparation of the ceramic thin film layer, and thus the resulting thickness is not too uniform, but the ceramic thin film of the present invention does not need to have a uniform thickness. In another preferred embodiment the organozirconium compound comprises at least one of biscyclopentadienyl or bis (methylcyclopentadienyl) zirconium dichloride, zirconium isooctanoate, zirconium 2-ethylhexanoate, zirconocene dichloride, tetrabenzylzirconium tetrakis (ethylmethylamino) zirconium (IV), zirconium bis [2- (2-benzothiazolyl) phenol ] zinc tetramethylacrylate n-propoxide, zirconium hexafluoro-acetylacetonate, zirconium bis (n-butylcyclopentadienyl) zirconium acetylacetonate, cyclopentadienyl zirconium trichloride, tetrakis (dimethylamino) zirconium, 1.1.1-trifluoroacetylacetonate, pentamethylcyclopentadienyl zirconium (IV) trichloride, zirconium tetrakis (2,2,6, 6-tetramethyl-3, 5-heptanedioate). The organic zirconium compound is selected, on one hand, a material basis is provided for zirconium oxide formed after sintering, and on the other hand, the organic ligand is oxidized into gas after high-temperature sintering and expands in a system to form a porous structure. The dosage of the carbon fiber and the pore-forming agent in the system can be reduced. On the other hand, the zirconium oxide formed by the zirconium compound has a cocatalyst effect, so that the use amount of platinum can be effectively reduced. In another preferred embodiment the organohafnide comprises at least one of biscyclopentadienyl or bis (methylcyclopentadienyl) zirconium dichloride, zirconium isooctanoate, zirconium 2-ethylhexanoate, zirconocene dichloride, tetrabenzylzirconium tetrakis (ethylmethylamino) zirconium (IV), hafnium acetylacetonate, hafnium (IV) trifluoromethanesulfonate. In yet another preferred embodiment, the yttrium compound comprises at least one of yttrium (III) isopropoxide, yttrium (III) trifluoromethanesulfonate, yttrium nitrate, yttrium (2,2,6, 6-tetramethyl-3, 5-heptanedionate). In yet another preferred embodiment, the compound of cerium includes at least one of cerium (III) carbonate, cerium (III) nitrate, cerium (III) acetate, cerium oxalate, cerium triflate.

In addition to carbon element carried by the ligand or other elements generating gas, carbon element is also needed to be supplemented to ensure that enough carbon source generates enough carbon dioxide gas to form a communicated pore network structure, so that the porosity and the specific surface area are improved, and the circulation and exchange of gas are facilitated. In a preferred embodiment, the diameter of the nano carbon fiber is 30-400nm, and the length of the nano carbon fiber is 2um-500 um; the pore-forming agent comprises at least one of nano carbon black, PS micro powder and PMMA micro powder, and the particle size of the pore-forming agent is 0.05-10 um; the fine carbon nanofibers and pore former powder are more easily oxidized to gas to form pores, and thus the particle size range is selected.

The embodiment of the invention also provides a catalytic electrode based on the ceramic film material. The catalytic electrode comprises the ceramic thin film material and a catalytic layer coated on the ceramic thin film layer in the ceramic thin film material, the catalytic electrode in the embodiment of the invention has a porous structure, and as shown in fig. 1, a scanning electron microscope image of the catalytic electrode with the porous structure in the embodiment of the invention is shown. The catalyst layer is prepared by sintering catalytic slurry which is prepared from 2.5-18% of organic platinum compound, 3.5-20% of nano carbon black, 4.5-12% of organic adhesive, 0.5-2.0% of dispersant and 70% of organic solvent by mass percent. The dispersing agent helps the catalyst to be uniformly dispersed in the initial stage, and the adhesive helps the catalyst to be adhered to the ceramic film layer in the initial stage. The ligand of the nano carbon black and the organic platinum, the adhesive and the dispersing agent are carbonized in the sintering process to form airflow, on one hand, a porous structure can be formed, and on the other hand, after other ingredients become gas, the formed platinum is in direct contact with the ceramic film layer to generate interaction, so that a catalytic system is formed. In a preferred embodiment, the catalytic layer has a thickness of 0.02um to 0.3 um. In the gas-solid phase reaction, the catalyst in contact requires a small amount of catalyst, and only a thin layer is required, and it can be made ultrathin theoretically for saving raw materials, but the thickness range is preferable because of the limitation of the process conditions. In another preferred embodiment, the platinum compound comprises at least one of a carbonyl complex of platinum, divinyldichloroplatinum, tetraammineplatinum nitrate, dinitrosoplatinum, bis (cyanophenyl) dichloroplatinum (II), tetrachloroplatinate tetraammineplatinate, bis (tri-tert-butylphosphine) platinum (0), platinum (II) acetylacetonate, tetrakis (triphenylphosphine) platinum, cis-dichlorobis (diethylsulfide) platinum (II), 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0). In still another preferred embodiment, the shape of the nano carbon black is at least one of dendritic, spherical and plate-like; the particle size of the nano carbon black is 80nm-500 nm. The use of carbon black here is, as described above, the effect of the gas-forming raw material described without repeating the description.

In another aspect, the embodiment of the present invention provides a method for preparing a catalytic electrode, including the following steps:

s01, dispersing 10-20% of organic zirconium compound, 0.3-2.8% of organic hafnium compound, 1.0-4.2% of yttrium and cerium compound, 3-5.5% of carbon nanofiber and 2.5-8.0% of carbon black in 70% of organic solvent to prepare ceramic slurry;

s02, coating the slurry on the substrate, and drying and sintering to obtain a ceramic thin film layer loaded on the substrate;

s03, dispersing 2.5-18% of organic platinum compound, 3.5-20% of nano carbon black, 4.5-12% of organic binder and 0.5-2.0% of dispersant in 70% of organic solvent by mass to prepare catalytic slurry, loading the catalytic slurry on the ceramic film layer, drying, calcining and sintering to obtain the catalytic electrode.

Specifically, in step S01, the organic solvent used includes one or more of absolute ethyl alcohol, DBE, methyl carbonate, ethyl acetate, and NMP.

Specifically, in step S02, a portion of volatile substances is removed gently by drying, then calcining, and finally sintering to form a ceramic thin film layer. The sintering treatment of the ceramic thin film layer is laser activation sintering treatment. The laser has higher energy, on one hand, the laser can provide high temperature required by sintering, and on the other hand, the laser can also activate the catalytic performance of the zirconia system.

Specifically, in step S03, the catalyst slurry is supported by a dip coating method. The ceramic film of the embodiment of the invention forms a porous structure, the large specific surface area of the ceramic film load substrate cannot be well utilized due to the poor coverage of the ceramic film by adopting a coating mode, the full coverage can be realized by adopting a dip coating method, and the thickness of the catalyst layer can be controlled by controlling the concentration of the slurry, so that the ceramic film can be adjusted to achieve the purpose of reducing the consumption of noble metal platinum so as to save the cost.

Specifically, in step S03, the sintering manner of the catalytic slurry is microwave sintering. The method is characterized in that the method carries out rapid sintering in a microwave sintering furnace, and utilizes the advantages of rapid heating speed of microwave sintering and simultaneous heating inside and outside to combine the ultrafine platinum particles with the surface of the ceramic, refine the crystal grains of the platinum particles and keep the surface activity of the nascent platinum.

In yet another aspect, embodiments of the present invention provide a solid fuel cell including the catalytic electrode. Thus inheriting the advantages of the catalytic electrode. On one hand, the catalyst has good stability brought by a ceramic film material, catalytic area brought by reaching specific surface area, and electrochemical reaction activity which is integrated with catalytic activity brought by zirconium oxide doped rare earth oxide. And then, the excellent catalytic performance of platinum on the surface is added, so that the solid fuel cell has good stability and good electrical performance, namely, the maximum voltage is high, and the energy conversion efficiency is high.

Example 1

The embodiment provides a ceramic film material which is prepared by the following method:

10 percent of dicyclopentadienyl or bis (methylcyclopentadienyl) zirconium dichloride and 2.8 percent of hafnium isooctanoate; 1.0% of yttrium nitrate, 1.0% of cerium oxalate, 5.5% of carbon fiber, 2.5% of nano carbon black and PS micro powder are dispersed in the balance percentage of methyl carbonate and fully ball-milled and dispersed to prepare ceramic slurry;

coating the ceramic slurry on a substrate, drying at 120 ℃, heating to 900 ℃ at the temperature rise speed of 3 ℃, heating and calcining in a box type sintering furnace in the air atmosphere, keeping the temperature for 0.5h, and finally performing laser activation sintering to obtain the ceramic film material.

The embodiment also provides a catalytic electrode which is prepared by the following method on the basis of the ceramic film material:

fully ball-milling and dispersing 3 mass percent of divinyl dichloroplatinum, 4 mass percent of nano carbon black, 8 mass percent of organic adhesive and 1 mass percent of dispersant in the balance of methyl carbonate to prepare catalytic slurry; the preparation process of the slurry comprises the steps of putting various components into a glass cup according to a proportion, fully stirring, then putting into a non-contact planetary stirring vacuum defoaming all-in-one machine, and preparing according to 3 steps of low-speed dispersion stirring, high-speed dispersion stirring and vacuum defoaming. The parameter data are: the vacuum degree of the non-contact planetary stirring and vacuum defoaming all-in-one machine is-0.095 MPa, the revolution speed is 60r/min during low-speed stirring, and the ratio of the revolution speed to the rotation speed is 1: 1; during high-speed stirring, the revolution speed is 1000r/min, and the ratio of the revolution speed to the rotation speed is 2: 1. Dip-coating the dispersed slurry on the ceramic thin-layer material, drying at 120 ℃ for 3 hours, heating to 600 ℃ at the temperature rise rate of 3 ℃, heating and calcining in a box-type sintering furnace in the air atmosphere, preserving heat for 0.5-2 hours, and then transferring into a microwave sintering furnace for rapid sintering at the sintering temperature of 900 ℃ for 60 minutes to obtain the catalytic electrode.

Example 2

zirconium isooctoate with the mass fraction of 20 percent and hafnium isooctoate with the mass fraction of 0.3 percent are mixed; dispersing 2.1% of yttrium (III) isopropoxide, 2.1% of cerium (III) carbonate, 3% of carbon fiber and 8% of PMMA micropowder in the balance of methyl carbonate, and fully performing ball milling dispersion to prepare ceramic slurry;

coating the ceramic slurry on a substrate, drying at 120 ℃, heating to 900 ℃ at the temperature rise speed of 3 ℃, heating and calcining in a box type sintering furnace in the air atmosphere, preserving heat for 2 hours, and finally performing laser activation sintering to obtain the ceramic film material.

fully ball-milling 18 percent of dinitroso diammine platinum, 3.5 percent of nano carbon black, 12 percent of organic adhesive and 2 percent of dispersant in the balance of methyl carbonate to prepare catalytic slurry; the preparation process of the slurry comprises the steps of putting various components into a glass cup according to a proportion, fully stirring, then putting into a non-contact planetary stirring vacuum defoaming all-in-one machine, and preparing according to 3 steps of low-speed dispersion stirring, high-speed dispersion stirring and vacuum defoaming. The parameter data are: the vacuum degree of the non-contact planetary stirring and vacuum defoaming all-in-one machine is-0.095 MPa, the revolution speed is 100r/min during low-speed stirring, and the ratio of the revolution speed to the rotation speed is 1: 1; during high-speed stirring, the revolution speed is 600r/min, and the ratio of the revolution speed to the rotation speed is 1: 1. Dip-coating the dispersed slurry on the ceramic thin-layer material, drying at 120 ℃ for 3 hours, heating to 600 ℃ at the temperature rise rate of 3 ℃, heating and calcining in a box-type sintering furnace in the air atmosphere, preserving heat for 2 hours, and then transferring to a microwave sintering furnace for rapid sintering at the sintering temperature of 900 ℃ for 20 minutes to obtain the catalytic electrode.

Example 3

16 mass percent of cyclopentadienyl zirconium trichloride, 16 mass percent of zirconium bis [2- (2-benzothiazolyl) phenol ] zinc tetra-n-propoxide, 2.8 mass percent of hafnium isooctanoate, tetrabenzyl zirconium tetra (ethyl methylamino) zirconium (IV) and hafnium (IV) trifluoromethanesulfonate; 1.4 percent of (2,2,6, 6-tetramethyl-3, 5-heptanedionate) yttrium, 0.8 percent of cerium oxalate and cerium trifluoromethanesulfonate, 5.5 percent of carbon fiber and PS micro powder are dispersed in the balance of ethanol and fully ball-milled and dispersed to prepare ceramic slurry;

coating the ceramic slurry on a substrate, drying at 120 ℃, heating to 900 ℃ at the heating rate of 3 ℃, heating and calcining in a box-type sintering furnace in the air atmosphere, keeping the temperature for 1.5h, and finally performing laser activation sintering to obtain the ceramic film material.

fully ball-milling and dispersing 10 mass percent of divinyl dichloroplatinum, acetylacetone platinum (II), tetrakis (triphenylphosphine) platinum and cis-dichlorobis (diethyl sulfide) platinum (II), 19 mass percent of nano carbon black, 12 mass percent of organic binder and 2 mass percent of dispersant in ethanol with the balance percent to prepare catalytic slurry; the preparation process of the slurry comprises the steps of putting various components into a glass cup according to a proportion, fully stirring, then putting into a non-contact planetary stirring vacuum defoaming all-in-one machine, and preparing according to 3 steps of low-speed dispersion stirring, high-speed dispersion stirring and vacuum defoaming. The parameter data are: the vacuum degree of the non-contact planetary stirring and vacuum defoaming all-in-one machine is-0.095 MPa, the revolution speed is 200r/min during low-speed stirring, and the ratio of the revolution speed to the rotation speed is 5: 1; when stirring at high speed, the revolution speed is 2000r/min, and the ratio of the revolution speed to the rotation speed is 6: 1. And dip-coating the slurry subjected to dispersion treatment on the ceramic thin-layer material, drying at 120 ℃ for 3 hours, heating to 600 ℃ at the temperature rise speed of 3 ℃, heating and calcining in an air atmosphere in a box-type sintering furnace, keeping the temperature for 2 hours, and then quickly sintering in a microwave sintering furnace at the sintering temperature of 200 ℃ for 120 minutes to obtain the catalytic electrode.

Example 4

20 percent of cyclopentadienyl zirconium trichloride, tetra (dimethylamino) zirconium, 1.1.1-zirconium trifluoroacetylacetonate and pentamethyl cyclopentadienyl zirconium (IV) trichloride, 1.8 percent of dichlorozirconocene, tetrabenzylzirconium tetra (ethylmethylamino) zirconium (IV), hafnium acetylacetonate and hafnium (IV) trifluoromethanesulfonate; 2.0% of yttrium (III) isopropoxide and yttrium (III) trifluoromethanesulfonate, 0.5% of cerium oxalate, 5.5% of carbon fibers, 2.5% of nano carbon black, PS micro powder and PMMA micro powder are dispersed in the balance of a mixed solvent of DBE and NMP (the solvent ratio is 2:3) to be fully ball-milled and dispersed to prepare ceramic slurry;

fully ball-milling and dispersing 2.5 mass percent of tetrakis (triphenylphosphine) platinum, 12 mass percent of nano carbon black, 12 mass percent of organic adhesive and 1.6 mass percent of dispersant in the balance percentage of mixed solvent (the solvent ratio is 1:2:3) of DBE, ethyl acetate and NMP to prepare catalytic slurry; the preparation process of the slurry comprises the steps of putting various components into a glass cup according to a proportion, fully stirring, then putting into a non-contact planetary stirring vacuum defoaming all-in-one machine, and preparing according to 3 steps of low-speed dispersion stirring, high-speed dispersion stirring and vacuum defoaming. The parameter data are: the vacuum degree of the non-contact planetary stirring and vacuum defoaming all-in-one machine is-0.095 MPa, the revolution speed is 200r/min during low-speed stirring, and the ratio of the revolution speed to the rotation speed is 1: 1; during high-speed stirring, the revolution speed is 1000r/min, and the ratio of the revolution speed to the rotation speed is 3: 1. Dip-coating the dispersed slurry on the ceramic thin-layer material, drying at 120 ℃ for 3 hours, heating to 600 ℃ at the temperature rise rate of 3 ℃, heating and calcining in a box type sintering furnace in the air atmosphere, preserving heat for 1.1 hour, and then transferring to a microwave sintering furnace for rapid sintering at the sintering temperature of 1100 ℃ for 60 minutes to obtain the catalytic electrode.

Example 5

18 mass percent of zirconium isooctanoate and 2-zirconium ethyl hexanoate, 0.8 mass percent of hafnium acetylacetonate and hafnium (IV) trifluoromethanesulfonate; dispersing 1.0% of yttrium nitrate, 2.2% of cerium trifluoromethanesulfonate, 4% of carbon fiber and 8% of nano carbon black in the balance of methyl carbonate, and fully performing ball-milling dispersion to prepare ceramic slurry;

fully ball-milling and dispersing 6% of tetramine platinum nitrate, 20% of nano carbon black, 6% of organic adhesive and 1.2% of dispersing agent in the balance of ethanol to prepare catalytic slurry; the preparation process of the slurry comprises the steps of putting various components into a glass cup according to a proportion, fully stirring, then putting into a non-contact planetary stirring vacuum defoaming all-in-one machine, and preparing according to 3 steps of low-speed dispersion stirring, high-speed dispersion stirring and vacuum defoaming. The parameter data are: the vacuum degree of the non-contact planetary stirring and vacuum defoaming all-in-one machine is-0.095 MPa, the revolution speed is 40r/min during low-speed stirring, and the ratio of the revolution speed to the rotation speed is 1: 3; during high-speed stirring, the revolution speed is 360r/min, and the ratio of the revolution speed to the rotation speed is 4: 1. Dip-coating the dispersed slurry on the ceramic thin-layer material, drying at 120 ℃ for 3 hours, heating to 600 ℃ at the temperature rise rate of 3 ℃, heating and calcining in a box-type sintering furnace in the air atmosphere, preserving heat for 1.5 hours, and then transferring to a microwave sintering furnace for rapid sintering at the sintering temperature of 950 ℃ for 70 minutes to obtain the catalytic electrode.

Performance testing of the catalytic electrodes of examples 1-5:

the performance index testing method comprises the following steps: electro-catalyst test method (GB/T20042.4-2009)

1. The test data of the Pt content is 0.06-0.1mg/cm²I.e., 0.06-0.1mg of platinum per square centimeter of catalytic electrode. The traditional Pt/C catalytic electrode is 0.3-0.6mg/cm²。

2. Electrochemical active area (ECA) test of 53.6-61.2m²/g。

3. Electrode catalytic performance: 550-650mA/cm²Is 2 times of that of the traditional Pt/C catalytic electrode.

4. Power density: the test data of 2-3kw/g Pt is that the fuel cell can generate 3kw of power per gram of Pt. The traditional Pt/C catalytic electrode is 0.4-0.73kw/g Pt

5. And (3) stability testing: 20000 cycles of accelerated aging test shows that the electrochemical active area attenuation rate is lower than 15%. The decay rate of the catalytic performance of the electrode is lower than 20 percent.

It can be known that the catalytic electrode prepared by the method can use less noble metal platinum, so that the cost is saved, all performances of the catalytic electrode are not reduced, and even some performances are obviously improved.

The performance data for specific examples 1-5 are shown in the following table:

	example 1	Example 2	Example 3	Example 4	Example 5
						Pt content mg/cm²	0.063	0.103	0.081	0.059	0.075
Electrochemical active area m²/g	60.3	53.6	58.1	61.2	59.2
						Electrocatalytic performance mA/cm²	563	657	609	555	583
Power density kw/g Pt	2.13	3.01	2.33	2.04	2.21
						Electrochemical active area decay rate	10.60％	14.70％	9.80％	11.90％	13.50％
Decay rate of catalytic performance of electrode	12.30％	19.30％	15.10％	16.60％	17.70％

Claims

1. A catalytic electrode comprises a ceramic film material and a catalytic layer, and is characterized in that: the ceramic thin film material comprises a substrate and a ceramic thin film layer loaded on the substrate; the ceramic film layer is prepared by sintering ceramic slurry prepared from 10-20% of organic zirconium compound, 0.3-2.8% of organic hafnium compound, 1.0-4.2% of yttrium and cerium compound, 3-5.5% of nano carbon fiber, 2.5-8.0% of pore-forming agent and 70% of organic solvent by mass;

the catalytic layer is coated on the ceramic thin film layer in the ceramic thin film material; the catalyst layer is prepared by sintering catalytic slurry prepared from 2.5-18% of organic platinum compound, 3.5-20% of nano carbon black, 4.5-12% of organic adhesive, 0.5-2.0% of dispersant and 70% of organic solvent by mass.

2. The catalytic electrode of claim 1, wherein: the thickness of the ceramic film layer is 0.5-20 μm.

3. The catalytic electrode of claim 1, wherein: the organozirconium compound comprises at least one of biscyclopentadienyl or bis (methylcyclopentadienyl) zirconium dichloride, zirconium isooctanoate, zirconium 2-ethylhexanoate, zirconocene dichloride, tetrabenzylzirconium tetrakis (ethylmethylamino) zirconium (IV), zirconium tetramethylacrylate bis [2- (2-benzothiazolyl) phenol ] zinc n-propoxide, zirconium hexafluoro-acetylacetonate, zirconium acetylacetonate bis (n-butylcyclopentadienyl) zirconium dichloride, cyclopentadienyl zirconium trichloride, tetrakis (dimethylamino) zirconium, 1.1.1. -zirconium trifluoroacetylacetonate, pentamethylcyclopentadienyl zirconium (IV), zirconium tetraethoxy tetrakis (2,2,6, 6-tetramethyl-3, 5-heptanedioate) zirconium; and/or

The organohafnide comprises at least one of biscyclopentadienyl or bis (methylcyclopentadienyl) zirconium dichloride, zirconium isooctanoate, zirconium 2-ethylhexanoate, zirconocene dichloride, tetrabenzylzirconium tetrakis (ethylmethylamino) zirconium (IV), hafnium acetylacetonate, hafnium (IV) trifluoromethanesulfonate; and/or

The yttrium compound comprises at least one of yttrium (III) isopropoxide, yttrium (III) trifluoromethanesulfonate, yttrium nitrate, yttrium (2,2,6, 6-tetramethyl-3, 5-heptanedionate); and/or

The cerium compound comprises at least one of cerium (III) carbonate, cerium (III) nitrate, cerium (III) acetate, cerium oxalate and cerium trifluoromethanesulfonate; and/or

The diameter of the nano carbon fiber is 30-400nm, and the length of the nano carbon fiber is 2-500 mu m; and/or

The pore-forming agent comprises at least one of nano carbon black, PS micro powder and PMMA micro powder, and the microscopic shape of the pore-forming agent is at least one of dendritic shape, spherical shape and sheet shape; the particle size of the pore-forming agent is 0.05-10 μm.

4. The catalytic electrode of claim 1, wherein: the thickness of the catalytic layer is 0.02-0.3 μm.

5. The catalytic electrode of claim 1, wherein: the platinum compound comprises at least one of a carbonyl complex of platinum, divinyl dichloroplatinum, tetraammineplatinum nitrate, dinitrosoplatinum, bis (cyanophenyl) dichloroplatinum (II), tetrachloroplatnum tetraammineplatinate, bis (tri-tert-butylphosphine) platinum (0), platinum (II) acetylacetonate, tetrakis (triphenylphosphine) platinum, cis-dichlorobis (diethylsulfide) platinum (II), 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0); and/or

6. A method for producing a catalytic electrode, for producing a catalytic electrode according to any one of claims 1 to 5; the preparation method of the catalytic electrode comprises the following steps:

dispersing 10-20% of organic zirconium compound, 0.3-2.8% of organic hafnium compound, 1.0-4.2% of yttrium and cerium compound, 3-5.5% of carbon nanofiber and 2.5-8.0% of carbon black in 70% of organic solvent to prepare ceramic slurry;

coating the slurry on the substrate, and drying, calcining and sintering the substrate to obtain a ceramic thin film layer loaded on the substrate;

the catalytic slurry prepared by dispersing 2.5-18% of organic platinum compound, 3.5-20% of nano carbon black, 4.5-12% of organic adhesive and 0.5-2.0% of dispersant in 35-60% of organic solvent is loaded on the ceramic film layer, and the catalytic electrode is obtained by drying, calcining and sintering.

7. The method of preparing a catalytic electrode according to claim 6, wherein: the sintering treatment of the ceramic thin film layer is laser activation sintering treatment.

8. The method of preparing a catalytic electrode according to claim 6, wherein: the loading mode of the catalytic slurry is a dip-coating method;

the sintering mode of the catalytic slurry is microwave sintering.

9. A solid fuel cell, characterized in that: comprising a catalytic electrode according to any one of claims 1 to 5.