CN108123156B - Preparation method of composite membrane electrode of fuel cell - Google Patents
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
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- 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
Abstract
The invention provides a preparation method of a composite membrane electrode of a fuel cell, which is characterized in that a layer of nitrogen-doped nano diamond particle film with high graphitization degree is deposited on the surface of a monocrystalline silicon substrate, strong acid is used for carrying out surface treatment on the film, the surface layer of the film is soaked in a cerium salt/lanthanide cobaltate mixed solution after filtration, the heat preservation is carried out for 24 hours after hydrothermal treatment, a precursor of a diamond-based SDC/perovskite type composite membrane electrode is obtained, and finally the composite membrane electrode is prepared through the procedures of filtration, drying, annealing and the like. According to the invention, the doped diamond is used as an electrode framework, the doped cerium oxide and the perovskite structure are compounded and then loaded on the diamond framework, and through the high thermal conductivity and the thermal stability of the diamond, the problem of poor thermal shock resistance of the traditional cerium oxide catalyst and cobaltate compounded is solved, and the defects of large internal resistance of a thin film and poor quality of the thin film caused by large difference of thermal expansion coefficients of a cerium oxide-based electrolyte and an electrode layer of the traditional perovskite structure oxide are effectively overcome.
Description
Technical Field
The invention relates to the field of fuel cell materials, in particular to a preparation method of a composite membrane electrode of a fuel cell.
Background
Because the traditional fossil fuel is not renewable and the environmental pollution caused in the using process is serious, the search for environment-friendly renewable energy is a serious task for people in the 21 st century. The Fuel cell (Fuel cell) is a novel energy technology, which directly converts chemical energy of Fuel into electric energy through electrochemical reaction, and the used Fuel is hydrogen-rich substances such as hydrogen, methanol and hydrocarbons, and has no pollution to the environment, high energy efficiency and high power density, so the Fuel cell has wide application prospect.
Solid Oxide Fuel Cells (SOFC) belong to the third generation Fuel cells, and are all-Solid-state chemical power generation devices which directly convert chemical energy stored in Fuel and oxidant into electric energy at medium and high temperature with high efficiency and environmental friendliness. The anode functions as a support in the thin-film SOFC, and also functions as a catalyst for the electrochemical reaction of the fuel and provides a reaction interface, and is an essential component of the fuel cell circuit system. The selection of electrode materials and the design of microstructure directly influence the working characteristics of the SOFC, and the performance of the electrode is strongly influenced by the microstructure, temperature, manufacturing process, cell structure and the like besides being related to the composition of the electrode.
Oxides of perovskite structure are of great interest to electrochemical workers because they can maintain stable structure and properties over a wide range of oxygen partial pressures and temperatures, and doped perovskite structure oxides can exhibit mixed conductor performance while having a catalytic effect on fuel oxidation. The traditional perovskite structure oxide such as strontium lanthanum cobaltate has higher oxygen ion conductivity and catalytic performance, the working temperature of the solid oxide fuel cell is mainly concentrated at 600-1000 ℃, and the internal resistance of the thin film is increased and the quality of the thin film is deteriorated due to large difference of thermal expansion coefficients of a cerium oxide-based electrolyte and an electrode layer.
Chinese invention patent application No. 201210090476.X discloses a material for a solid oxide fuel cell, and a cathode and a solid oxide fuel cell containing the material. By doping a transition metal element and/or a lanthanoid element to the perovskite type oxide, high ionic conductivity and a low thermal expansion coefficient can be achieved even in a low temperature region. The scheme minimizes the interlayer thermal mismatch of the battery and improves the stability of the battery by doping the perovskite type oxide, thereby improving the durability of the battery. The scheme minimizes the interlayer thermal mismatch of the battery and improves the stability of the battery by doping the perovskite type oxide, thereby improving the durability of the battery. However, when the transition metal element and/or the lanthanide element is doped into the perovskite type oxide, the purity and the structural stability of the perovskite structure phase structure are easily affected by the doping amount and the preparation atmosphere, the preparation of the pure phase is difficult, and the phase change is easy to occur under the high-temperature condition.
Chinese patent application No. 201510324997.0 discloses a double perovskite type intermediate temperature solid oxide fuel cell cathode material and a preparation method thereof, wherein required alkaline earth nitrate and the like and a complexing agent are fully mixed in an aqueous solution to obtain gel, and the dried gel is calcined at 500-700 ℃ and 800-950 ℃ respectively. Sintering the calcined powder at 1100-1300 ℃ for 10-20 hours to obtain the corresponding single-phase double perovskite cathode material. The double perovskite structure provided by the invention reduces the thermal expansion coefficient of the cathode material, solves the problem of unstable structure of single Co-based and Fe-based perovskite oxides at high temperature, and improves the stability of the material. However, the double perovskite type material has complex composition, needs high temperature, obtains a better component structure through long-time sintering treatment, and has the problem of low thermal conductivity in application. Therefore, the development of a membrane electrode material with simple preparation process and stable high-temperature structure and performance has very important practical significance for improving the stability of the electrolyte layer and the electrode layer of the membrane electrode in the repeated hot start process.
Disclosure of Invention
Aiming at the defects that the perovskite structure electrode material structure in the prior art is high in preparation difficulty, low in heat conductivity and easy to change phase under a high-temperature condition, the invention provides the preparation method of the composite membrane electrode of the fuel cell, which reduces the preparation difficulty and solves the problem that the traditional cerium oxide electrolyte layer and the cobaltate perovskite structure layer are poor in thermal shock resistance after being compounded.
In order to solve the problems, the invention adopts the following technical scheme:
a method for preparing a composite membrane electrode of a fuel cell adopts a monocrystalline silicon substrate as a precursor substrate of the composite membrane electrode, and comprises the following steps:
(1) preparing a nitrogen-doped nano-diamond film on the surface of a monocrystalline silicon substrate by adopting plasma-assisted chemical vapor deposition, wherein the thickness of the nitrogen-doped nano-diamond film is 20-800 microns;
(2) treating the surface of the nitrogen-doped nano-diamond film, immersing the nitrogen-doped nano-diamond film in strong acid, performing surface treatment, and filtering to obtain an activated nitrogen-doped nano-diamond film;
(3) immersing the activated nitrogen-doped nano diamond film in a mixed solution of cerium salt, lanthanum salt, cobalt salt and samarium salt, adding citric acid serving as a complexing agent, dropwise adding NaOH and Na2CO3 mixed in equal volume into the mixed solution, adjusting the pH value to be alkalescent, carrying out hydrothermal treatment at 75-90 ℃ for 24-36 hours until precipitates are completely separated out, and obtaining a precursor of the diamond-based SDC/perovskite type composite film electrode, wherein the SDC = SmxCE1-xO2, and x is more than 0 and less than 0.5;
(4) and filtering and washing the precursor of the diamond-based SDC/perovskite type composite membrane electrode, drying, and annealing to obtain the diamond-based SDC/perovskite type composite membrane electrode.
Preferably, the plasma-assisted chemical vapor deposition uses acetylene gas as a carbon source, nitrogen as a nitrogen source, microwave plasma as a plasma source, the microwave power is 1-9 kW, and the deposition pressure is 0.2-20 Pa.
Preferably, the content of SP2 bonds in the nitrogen-doped nano-diamond film reaches 60-75%.
Preferably, the strong acid is one of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid and perchloric acid with the pH of 2-4.
Preferably, the strong acid treatment time is 20 to 120 minutes.
Preferably, the ion concentration ratio of the cerium salt, the lanthanum salt, the cobalt salt and the samarium salt is 1.2-2.7: 1: 1: 0.01-0.03.
Preferably, the cerium salt is one of cerium chloride, cerium bromide and cerium nitrate, the lanthanum salt is one of lanthanum chloride, lanthanum bromide and lanthanum nitrate, the cobalt salt is one of cobalt chloride, cobalt bromide and cobalt nitrate, and the samarium salt is one of samarium chloride, samarium bromide and samarium nitrate.
Preferably, the drying treatment is drying at 70-80 ℃ for 2-5 hours.
Preferably, the annealing treatment is crystallization treatment at 350-600 ℃ for 12-16 hours.
Aiming at the defects that the perovskite structure electrode material in the prior art is high in structure preparation difficulty, low in heat conductivity and easy to phase change at high temperature, the invention provides a preparation method of a composite membrane electrode of a fuel cell. The doped diamond is used as an electrode framework, the doped cerium oxide and the perovskite structure are compounded and then loaded on the diamond framework, the problem of poor thermal shock resistance of the traditional cerium oxide catalyst and cobaltate compounded is solved through the high thermal conductivity and the thermal stability of the diamond, and the disadvantages that the internal resistance of a thin film is increased and the quality of the thin film is poor due to the large difference of the thermal expansion coefficients of a cerium oxide-based electrolyte and an electrode layer of the traditional perovskite structure oxide are effectively overcome.
The performance of the cell material obtained by mixing the composite membrane electrode of the fuel cell prepared by the invention and lanthanide doped perovskite oxide is tested at the test temperature of 800 ℃, as shown in table 1.
Table 1:
compared with the prior art, the invention provides a preparation method of a composite membrane electrode of a fuel cell, which has the outstanding characteristics and excellent effects that:
according to the invention, the doped diamond is used as an electrode framework, the doped cerium oxide and the perovskite structure are compounded and then loaded on the diamond framework, and the high thermal conductivity and the thermal stability of the diamond are utilized to well match with the cerium oxide-based electrolyte structure, so that the defects of large internal resistance of a thin film and poor quality of the thin film caused by large difference of thermal expansion coefficients of the cerium oxide-based electrolyte and an electrode layer in the traditional perovskite structure oxide are effectively overcome. The preparation method has great process adjustability, can be adjusted according to different electrolyte materials, and has the advantages of low cost, good process repeatability, simple process and the like.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Preparing a nitrogen-doped nano-diamond film on the surface of a monocrystalline silicon substrate by adopting plasma-assisted chemical vapor deposition, wherein acetylene gas is used as a carbon source, nitrogen is used as a nitrogen source, and the gas flow ratio is 20: 1, microwave plasma is taken as a plasma source, the microwave power is 1kW, the deposition pressure is 20 Pa, the thickness of the prepared nitrogen-doped nano-diamond film is 20 micrometers, and the SP2 bond content of the nitrogen-doped nano-diamond film reaches 75%;
(2) treating the surface of the nitrogen-doped nano-diamond film, immersing the surface in concentrated sulfuric acid with the pH value of 2, performing surface treatment for 20 minutes, and filtering to obtain an activated nitrogen-doped nano-diamond film;
(3) immersing the activated nitrogen-doped nano-diamond film in a solution prepared from cerium chloride, lanthanum chloride, samarium chloride and cobalt chloride, wherein the concentration ratio of each cation is 1.2: 1: 1: 0.03, adding a proper amount of complexing agent citric acid, and mixing equal volumes of NaOH and Na2CO3Dropwise adding into the mixed solution, adjusting pH to alkalescence, carrying out hydrothermal treatment at 75 ℃ for 36 hours until precipitate is completely separated out, and obtaining a precursor of the diamond-based SDC/perovskite type composite membrane electrode, wherein SDC = SmxCe1-xO2,0＜x＜0.5；
(4) And filtering and washing the precursor of the diamond-based SDC/perovskite type composite membrane electrode, drying for 5 hours at 70 ℃, and then performing crystallization treatment for 12 hours at 350 ℃ for annealing treatment to prepare the diamond-based SDC/perovskite type composite membrane electrode.
The conductivity was measured using a conductivity meter model DDSJ-308F, DIL402PC from NETZSCH Group as a device for measuring the coefficient of thermal expansion, and the measured result was compared with the electrolyte CeO2Sintering the materials together, assembling the materials into a single cell, measuring the electrochemical performance, and taking the test temperature as 800 ℃, hydrogen as fuel and air as oxidant, wherein the measured parameters are shown in Table 2.
Example 2
(1) Preparing a nitrogen-doped nano-diamond film on the surface of a monocrystalline silicon substrate by adopting plasma-assisted chemical vapor deposition, wherein acetylene gas is used as a carbon source, nitrogen is used as a nitrogen source, and the gas flow ratio is 30: 1, microwave plasma is taken as a plasma source, the microwave power is 5kW, the deposition pressure is 10 Pa, the thickness of the prepared nitrogen-doped nano-diamond film is 240 micrometers, and the content of SP2 bonds of the nitrogen-doped nano-diamond film reaches 70%;
(2) treating the surface of the nitrogen-doped nano-diamond film, immersing the nitrogen-doped nano-diamond film in concentrated nitric acid with the pH value of 3, performing surface treatment for 20 minutes, and filtering to obtain an activated nitrogen-doped nano-diamond film;
(3) immersing the activated nitrogen-doped nano-diamond film in a solution prepared from cerium bromide, lanthanum bromide, samarium bromide and cobalt bromide, wherein the concentration ratio of each cation is 1.5: 1: 1: 0.01, adding a proper amount of complexing agent citric acid, and mixing equal volumes of NaOH and Na2CO3Dropwise adding into the mixed solution, adjusting pH to alkalescence, carrying out hydrothermal treatment at 85 ℃ for 30 hours until precipitate is completely separated out, and obtaining the precursor of the diamond-based SDC/perovskite type composite membrane electrode, wherein SDC = SmxCe1-xO2,0＜x＜0.5；
(4) And filtering and washing the precursor of the diamond-based SDC/perovskite type composite membrane electrode, drying for 2 hours at 80 ℃, and performing crystallization treatment for 15 hours at 450 ℃ for annealing treatment to prepare the diamond-based SDC/perovskite type composite membrane electrode.
The conductivity was measured using a conductivity meter model DDSJ-308F, DIL402PC from NETZSCH Group as a device for measuring the coefficient of thermal expansion, and the measured result was compared with the electrolyte CeO2Sintering the components together, assembling the components into a single cell, measuring the electrochemical performance, and measuring the test temperature at 850 ℃, hydrogen as fuel and air as oxidant, wherein the measured parameters are shown in Table 2.
Example 3
(1) Preparing a nitrogen-doped nano-diamond film on the surface of a monocrystalline silicon substrate by adopting plasma-assisted chemical vapor deposition, wherein acetylene gas is used as a carbon source, nitrogen is used as a nitrogen source, and the gas flow ratio is 25: 1, microwave plasma is taken as a plasma source, the microwave power is 4kW, the deposition pressure is 5 Pa, the thickness of the prepared nitrogen-doped nano-diamond film is 500 micrometers, and the SP2 bond content of the nitrogen-doped nano-diamond film reaches 75%;
(2) processing the surface of the nitrogen-doped nano-diamond film, immersing the surface of the nitrogen-doped nano-diamond film in concentrated hydrochloric acid with pH of 4, processing the surface for 120 minutes, and filtering to obtain an activated nitrogen-doped nano-diamond film;
(3) immersing the activated nitrogen-doped nano-diamond film in a solution prepared from cerium chloride, lanthanum chloride, samarium chloride and cobalt chloride, wherein the concentration ratio of each cation is 2.2: 1: 1: 0.02, adding a proper amount of complexing agent citric acid, and mixing equal volumes of NaOH and Na2CO3Dropwise adding into the mixed solution, adjusting pH to alkalescence, carrying out hydrothermal treatment at 80 ℃ for 26 hours until precipitate is completely separated out, and obtaining a precursor of the diamond-based SDC/perovskite type composite membrane electrode, wherein SDC = SmxCe1-xO2,0＜x＜0.5；
(4) And filtering and washing the precursor of the diamond-based SDC/perovskite type composite membrane electrode, drying for 4 hours at 75 ℃, and performing crystallization treatment for 15 hours at 350 ℃ for annealing treatment to prepare the diamond-based SDC/perovskite type composite membrane electrode.
The conductivity was measured using a conductivity meter model DDSJ-308F, DIL402PC from NETZSCH Group as a device for measuring the coefficient of thermal expansion, and the measured result was compared with the electrolyte CeO2Sintering the materials together, assembling the materials into a single cell, measuring the electrochemical performance, and taking the test temperature as 800 ℃, hydrogen as fuel and air as oxidant, wherein the measured parameters are shown in Table 2.
Example 4
(1) Preparing a nitrogen-doped nano-diamond film on the surface of a monocrystalline silicon substrate by adopting plasma-assisted chemical vapor deposition, wherein acetylene gas is used as a carbon source, nitrogen is used as a nitrogen source, and the gas flow ratio is 20: 1, microwave plasma is taken as a plasma source, the microwave power is 1kW, the deposition pressure is 20 Pa, the thickness of the prepared nitrogen-doped nano-diamond film is 20 micrometers, and the SP2 bond content of the nitrogen-doped nano-diamond film reaches 75%;
(2) treating the surface of the nitrogen-doped nano-diamond film, immersing the surface in concentrated sulfuric acid with the pH value of 2, performing surface treatment for 20 minutes, and filtering to obtain an activated nitrogen-doped nano-diamond film;
(3) immersing the activated nitrogen-doped nano-diamond film in a solution prepared from cerium chloride, lanthanum chloride, samarium chloride and cobalt chloride, wherein the concentration ratio of each cation is 1.2: 1: 1: 0.03, adding a proper amount of complexing agent citric acid, and mixing equal volumes of NaOH and Na2CO3Dropwise adding into the mixed solution, adjusting pH to alkalescence, carrying out hydrothermal treatment at 75 ℃ for 36 hours until precipitate is completely separated out, and obtaining a precursor of the diamond-based SDC/perovskite type composite membrane electrode, wherein SDC = SmxCe1-xO2,0＜x＜0.5；
(4) And filtering and washing the precursor of the diamond-based SDC/perovskite type composite membrane electrode, drying for 5 hours at 700 ℃, and then performing crystallization treatment for 12 hours at 350 ℃ for annealing treatment to prepare the diamond-based SDC/perovskite type composite membrane electrode.
The conductivity was measured using a conductivity meter model DDSJ-308F, DIL402PC from NETZSCH Group as a device for measuring the coefficient of thermal expansion, and the measured result was compared with the electrolyte CeO2Sintering the materials together, assembling the materials into a single cell, measuring the electrochemical performance, and taking the test temperature as 800 ℃, hydrogen as fuel and air as oxidant, wherein the measured parameters are shown in Table 2.
Example 5
(1) Preparing a nitrogen-doped nano-diamond film on the surface of a monocrystalline silicon substrate by adopting plasma-assisted chemical vapor deposition, wherein acetylene gas is used as a carbon source, nitrogen is used as a nitrogen source, and the gas flow ratio is 20: 1, microwave plasma is taken as a plasma source, the microwave power is 1kW, the deposition pressure is 20 Pa, the thickness of the prepared nitrogen-doped nano-diamond film is 20 micrometers, and the SP2 bond content of the nitrogen-doped nano-diamond film reaches 75%;
(2) treating the surface of the nitrogen-doped nano-diamond film, immersing the surface in concentrated sulfuric acid with the pH value of 2, performing surface treatment for 20 minutes, and filtering to obtain an activated nitrogen-doped nano-diamond film;
(3) immersing the activated nitrogen-doped nano-diamond film in a solution prepared from cerium chloride, lanthanum chloride, samarium chloride and cobalt chloride, wherein the concentration ratio of each cation is 1.2: 1: 1: 0.03, adding a proper amount of complexing agent citric acid, and mixing equal volumes of NaOH and Na2CO3Dropwise adding into the mixed solution, adjusting pH to alkalescence, carrying out hydrothermal treatment at 75 ℃ for 36 hours until precipitate is completely separated out, and obtaining a precursor of the diamond-based SDC/perovskite type composite membrane electrode, wherein SDC = SmxCe1-xO2,0＜x＜0.5；
(4) And filtering and washing the precursor of the diamond-based SDC/perovskite type composite membrane electrode, drying for 5 hours at 700 ℃, and then performing crystallization treatment for 12 hours at 350 ℃ for annealing treatment to prepare the diamond-based SDC/perovskite type composite membrane electrode.
The conductivity was measured using a conductivity meter model DDSJ-308F, DIL402PC from NETZSCH Group as a device for measuring the coefficient of thermal expansion, and the measured result was compared with the electrolyte CeO2Sintering the materials together, assembling the materials into a single cell, measuring the electrochemical performance, and taking the test temperature as 800 ℃, hydrogen as fuel and air as oxidant, wherein the measured parameters are shown in Table 2.
Comparative example 1
(1) Taking Ba (NO)3)2，Sr(NO3)2，Co(NO3)2·6H2O, Fe(NO3)3·9H2O，Mn(NO3)2·6H2O raw material powder is mixed according to the weight ratio of 0.5: 0.5: weighing the five raw materials according to a molar ratio of 0.2:0.3, adding the five raw materials into an EDTA-ammonia water solution, mixing, heating to 80 ℃, and uniformly mixing the mixed solution to prepare precursor gel;
(2) calcining the precursor gel for 4 hours in a sectional manner at the temperature of 600 ℃ to remove organic matters. Then placing the mixture in a high temperature furnace, raising the temperature at the speed of 5 ℃/min, preserving the heat at 1100 ℃ for 4h, and then lowering the temperature to room temperature at the speed of 5 ℃/min to obtain Ba0.5Sr0.5Co0.8-xFe0.2MnxO3-δ；
The conductivity was measured using a DDSJ-308F conductivity meter, DIL402PC from NETZSCH Group as a thermal expansion coefficient measuring instrument, and assembled into a single cell after the test, the perovskite type electrode material prepared in the comparative example was formulated into a slurry and coated on an electrolyte layer to construct a single cell, the electrochemical properties were measured, the test temperature was 800 ℃, hydrogen was used as fuel, air was used as oxidant, and the measured parameters were as shown in Table 2.
TABLE 2
Claims (9)
1. A preparation method of a composite membrane electrode of a fuel cell is characterized in that a single crystal silicon substrate is adopted as a precursor substrate of the composite membrane electrode, and the preparation method specifically comprises the following steps:
(1) preparing a nitrogen-doped nano-diamond film on the surface of a monocrystalline silicon substrate by adopting plasma-assisted chemical vapor deposition, wherein the thickness of the nitrogen-doped nano-diamond film is 20-800 microns;
(2) treating the surface of the nitrogen-doped nano-diamond film, immersing the nitrogen-doped nano-diamond film in strong acid, performing surface treatment, and filtering to obtain an activated nitrogen-doped nano-diamond film;
(3) immersing the activated nitrogen-doped nano-diamond film in a mixed solution of cerium salt, lanthanum salt, cobalt salt and samarium salt, adding citric acid serving as a complexing agent, and mixing NaOH and Na with equal volume2CO3Dropwise adding the mixture into the mixed solution, adjusting the pH value to be alkalescent, carrying out hydrothermal treatment at 75-90 ℃ for 24-36 hours until precipitates are completely separated out, and obtaining a precursor of the diamond-based SDC/perovskite type composite membrane electrode, wherein SDC = SmxCe1-xO2, and x is more than 0 and less than 0.5;
(4) and filtering and washing the precursor of the diamond-based SDC/perovskite type composite membrane electrode, drying, and annealing to obtain the diamond-based SDC/perovskite type composite membrane electrode.
2. The method of claim 1, wherein the plasma assisted chemical vapor deposition uses acetylene gas as a carbon source, nitrogen as a nitrogen source, microwave plasma as a plasma source, microwave power is 1-9 kW, and deposition pressure is 0.2-20 Pa.
3. The method of claim 1, wherein the nitrogen-doped nanodiamond thin film has an SP2 bond content of 60-75%.
4. The method of claim 1, wherein the strong acid is one of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, and perchloric acid having a pH of 2 to 4.
5. The method of claim 1, wherein the treatment time of the strong acid is 20-120 minutes.
6. The method of claim 1, wherein the ratio of the concentrations of the cations of the cerium salt, lanthanum salt, cobalt salt, and samarium salt is 1.2-2.7: 1: 1: 0.01-0.03.
7. The method of claim 1, wherein the cerium salt is one of cerium chloride, cerium bromide and cerium nitrate, the lanthanum salt is one of lanthanum chloride, lanthanum bromide and lanthanum nitrate, the cobalt salt is one of cobalt chloride, cobalt bromide and cobalt nitrate, and the samarium salt is one of samarium chloride, samarium bromide and samarium nitrate.
8. The method of claim 1, wherein the drying is performed at 70-80 ℃ for 2-5 hours.
9. The method for preparing a composite membrane electrode of a fuel cell as claimed in claim 1, wherein the annealing treatment is crystallization treatment at 350-600 ℃ for 12-16 hours.
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