CN113451588A - Symbiotic fuel cell anode and preparation method and application thereof - Google Patents
Symbiotic fuel cell anode and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a symbiotic fuel cell anode and a preparation method and application thereof, wherein the symbiotic fuel cell anode comprises a perovskite matrix with a porous structure and Ni-Co-Fe ternary nano alloy particles generated in situ on the surface of the perovskite matrix after reduction treatment, and the perovskite matrix has a chemical formula of (La)0.6Sr0.4)0.95Fe0.7Co0.1Ni0.1Mo0.1O3‑δ. The symbiotic fuel cell anode provided by the invention is characterized in that a plurality of active transition metals are introduced into the B site under control, and then Ni-Co-Fe nanoparticles are precipitated in situ in a reducing atmosphere, so that the ternary alloy nanoparticles can effectively improve the catalytic activity of the anode, and when the symbiotic fuel cell anode is used for hydrocarbon fuels, the uniformly precipitated Ni-Co-Fe nanoparticles generateThe catalyst grows on the surface of a perovskite matrix, has good catalytic performance and anti-carbon deposition capability, and finally successfully realizes the efficient preparation of ethylene and the high-power output of electric energy.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a symbiotic fuel cell anode and a preparation method and application thereof.
Background
The problems of environmental pollution, energy transitional consumption and the like are increasingly serious, and the development and the use of a novel energy conversion technology are urgently needed. The continuous development of shale gas provides an effective energy source for society, wherein ethane has great use value as one of main components in the shale gas. Due to the similarity of structures, the preparation of ethylene from ethane is an effective way to use ethane as a resource at present, wherein ethylene is used as a main raw material for producing polymers in the chemical industry, and has great demand and utilization value. However, the main way of preparing ethylene in industry is to prepare ethylene by cracking ethane at high temperature, and this process has the problem of high energy consumption and increases production cost, so how to prepare ethylene with high efficiency and energy saving is a thermoelectric currently studied.
Compared with the oxygen-free dehydrogenation, the oxidative dehydrogenation of ethane to prepare ethylene has lower Gibbs free energy and can be performed spontaneously. However, the production of greenhouse gases by deep oxidation inevitably occurs when ethane is contacted with oxygen, increasing the cost of product separation. Therefore, when ethane is used as fuel, oxidation reaction occurs on the anode side to obtain ethylene, and reduction reaction of oxygen occurs on the cathode side, the dense electrolyte separates ethane from oxygen, deep oxidation is avoided, selectivity of ethylene is improved, and power generation is performed by using protons obtained by cracking ethane, so that co-generation of ethylene and electric energy can be realized.
However, when using hydrocarbon fuel, the anode catalyst has the problems of low catalytic activity, carbon deposition and the like, excessive carbon deposition can lead to the deactivation of the anode catalyst, and the low catalytic activity is difficult to crack ethane, which causes the inefficiency of the battery performance.
Therefore, the development and preparation technology of the existing anode catalyst still needs to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a symbiotic fuel cell anode and a preparation method and application thereof, and aims to solve the problems of low catalytic activity and easy carbon deposition of the existing symbiotic fuel cell anode.
The technical scheme of the invention is as follows:
the intergrowth type fuel cell anode comprises a perovskite matrix with a porous structure and Ni-Co-Fe ternary nano alloy particles which are subjected to reduction treatment and generated in situ on the surface of the perovskite matrix, wherein the perovskite matrix has a chemical formula of (La)0.6Sr0.4)0.95Fe0.7Co0.1Ni0.1Mo0.1O3-δ。
The anode of the symbiotic fuel cell, wherein the particle size of the Ni-Co-Fe ternary nano alloy particles is 20-25 nm.
A method of making a symbiotic fuel cell anode comprising the steps of:
lanthanum nitrate, strontium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate and ammonium molybdate are dissolved in deionized water with nitric acid to form a mixed solution, then citric acid and EDTA are added as complexing agents, the pH value is adjusted to a preset value, combustion treatment is carried out after stirring, and the perovskite matrix with the porous structure is prepared, wherein the chemical formula of the perovskite matrix is (La)0.6Sr0.4)0.95Fe0.7Co0.1Ni0.1Mo0.1O3-δ；
Heating and reducing the perovskite matrix in a reducing atmosphere to prepare a symbiotic fuel cell anode material;
dissolving the symbiotic fuel cell anode material in an organic solvent to prepare symbiotic fuel cell slurry;
and preparing the intergrowth type fuel cell slurry into layers to obtain the intergrowth type fuel cell anode.
The method for producing an anode for a cogeneration type fuel cell, wherein the predetermined value is 7 to 8.
The preparation method of the symbiotic fuel cell anode comprises the following steps of calcining at the temperature of 900-1100 ℃ for 4-6 h.
The preparation method of the symbiotic fuel cell anode comprises the steps of heating and reducing at the temperature of 800-850 ℃ for 2-5 h.
The preparation method of the symbiotic fuel cell anode comprises the step of preparing a catalyst by using a catalyst, wherein the catalyst is a metal oxide, and the catalyst is a metal oxide.
The preparation method of the symbiotic fuel cell anode comprises the following steps of dissolving the symbiotic fuel cell anode material in an organic solvent to prepare symbiotic fuel cell slurry:
mixing the anode material of the symbiotic fuel cell with polyethylene glycol, adding organic alcohol, carrying out ball milling for 6-12h, completely drying the organic alcohol, and uniformly grinding to obtain the symbiotic fuel cell slurry.
Use of a symbiotic fuel cell anode, wherein said symbiotic fuel cell anode of the invention is used to prepare a symbiotic fuel cell.
The application of the anode of the symbiotic fuel cell comprises the proton conductor electrolyte, the cathode and the anode which are respectively arranged at two sides of the solid electrolyte, and the anode is the anode of the symbiotic fuel cell.
Has the advantages that: the symbiotic fuel cell anode provided by the invention has the advantages that various active transition metals are introduced into the B site under the control, and then Ni-Co-Fe nanoparticles are precipitated in situ in a reducing atmosphere, so that the ternary alloy nanoparticles can effectively improve the catalytic activity of the anode, and when the ternary alloy nanoparticles are used for hydrocarbon fuels, the uniformly precipitated Ni-Co-Fe nanoparticles grow on the surface of a perovskite matrix, so that the ternary alloy nanoparticles have good catalytic performance and carbon deposition resistance, and finally the efficient preparation of ethylene and the high power output of electric energy are successfully realized.
Drawings
Fig. 1 is a schematic structural diagram of a cogeneration fuel cell according to the present invention.
Fig. 2 is an XRD pattern before and after LSFCNM anode reduction.
Fig. 3 is SEM images before and after reduction of the LSFCNM anode.
Fig. 4 is TEM images of LSFCNM anode before and after reduction.
Fig. 5 is a graph of the electrical conductivity of LSFCNM anode at different temperatures in a reducing atmosphere.
FIG. 6 is an impedance spectrum of an LSFCNM/BZCY (300 μm)/LSFCNM symmetrical cell in a hydrogen atmosphere at different temperatures.
FIG. 7 is a graph of the electrochemical performance of LSFCNM/BZCY (300 μm)/LSCF-SDC cells tested at different temperatures in hydrogen and ethane atmospheres.
FIG. 8 is a stability curve for a cell operating at 750 ℃ at a constant pressure of 0.6V, with an ethane flow rate of 30 ml/min.
Fig. 9 shows the ethane conversion and ethylene selectivity produced by the anode reaction of a fuel cell at 650-750 ℃ under open circuit and operating conditions.
Detailed Description
The invention provides a symbiotic fuel cell anode and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. 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 method has very important practical value for realizing efficient clean conversion of the hydrocarbon fuel, and is an important means for realizing effective utilization of the shale gas. At present, shale gas mainly contains low-carbon species such as methane, ethane, propane and the like, and if the hydrocarbon fuels are efficiently converted into energy and high-value chemicals, the shale gas has important significance for the problems of energy utilization, environmental pollution and the like. In consideration of the low energy conversion efficiency and serious environmental pollution in the conventional steam cracking mode, the development of the solid oxide fuel cell capable of directly using the hydrocarbon fuel can break through the limitation of Carnot cycle to directly generate electricity, and the energy conversion utility is effectively improved. When the conventional oxygen ion conductor SOFC is used, the deep oxidation of hydrocarbon fuel to generate CO and CO is inevitable2And compared with the prior art, the proton conductor SOFC can separate the hydrocarbon fuel from an oxygen source, avoid direct contact with the oxygen and is more environment-friendly. Meanwhile, protons generated by the anode are utilized in situ, and theoretically, the conversion efficiency is higher.
When proton conductor SOFCs are used, they are suitable for operation at medium and low temperatures due to lower activation energy. Therefore, the proton conductor electrolyte is beneficial to reducing the working temperature, thereby reducing the energy consumption, and the proton conductor SOFC is widely concerned by researchers in recent years. The current proton conductor fuel cell is mainly an anode-supported fuel cell with NiO as the anode, however, when using hydrocarbon fuel, NiO inevitably causes carbon deposition and thus causes catalyst deactivation. Therefore, the proton conductor fuel cell supported by the electrolyte can replace the anode with a catalyst with the carbon deposition resistance, thereby ensuring the normal operation of the fuel cell. When ethane is used as fuel, the anodic oxidation of ethane and the cathodic oxygen reduction process constitute an efficient electrochemical conversion pathway, avoiding direct contact of ethane with oxygen and potential deep oxidation processes. Protons generated by the ethane dehydrogenation reaction on the anode side are used to generate electricity and migrate to the cathode, thereby promoting the forward reaction. And water vapor is generated at the cathode, so that the process becomes a clean and efficient conversion path. The co-production of electric energy and ethylene has very favorable economic value and becomes a potential technology for the industrial production of ethylene and electric power.
The key to the efficient implementation of this process is the development of hydrocarbon fuel anode catalysts with excellent catalytic activity and anti-carbon deposition capabilities. The perovskite structure anode has rich oxygen vacancy content, is very suitable to be used as a channel for ion migration, and therefore has good catalytic activity. However, direct contact between the a-site metal located on the perovskite surface and the fuel gas limits catalytic activity, resulting in lower catalytic activity than nickel-based anodes. Researches find that the active sites of the catalyst can be effectively improved by precipitating the nano particles in situ, and meanwhile, the transformation of lattice oxygen to vacancy oxygen can be promoted by in-situ separation of the B-site active metal and the perovskite structure, so that the reaction activity and the stability of the catalyst are effectively improved.
Based on the structure, the invention provides a symbiotic fuel cell anode which comprises a perovskite matrix with a porous structure and Ni-Co-Fe ternary nano alloy particles generated in situ on the surface of the perovskite matrix after reduction treatment, wherein the perovskite matrix has a chemical formula of (La)0.6Sr0.4)0.95Fe0.7Co0.1Ni0.1Mo0.1O3-δ。
The symbiotic fuel cell anode provided by the present embodiment can be used to prepare a symbiotic fuel cell comprising a solid electrolyte and, on either side of the solid electrolyte, a symbiotic fuel cell anode (LSFCNM anode) and cathode, as shown in fig. 1, which has high power and high ethane conversion. In particular, efficient and stable operation under hydrocarbon fuel is a fatal problem of SOFC, and the stability of the anode catalyst has a great influence on the continuous operation of the cell. How to ensure that the anode keeps stable structure under the reducing atmosphere is a problem to be solved. Based on this, the embodiment performs a-site defect treatment and B-site active transition metal ion CO-doping on the LSFCNM perovskite structure, so as to ensure the structure and valence state balance of the anode, and simultaneously, the in-situ precipitated nanoparticles effectively improve the catalytic performance, and can be used as a fuel and CO-free for SOFC supported by proton conductor electrolyte2Discharging to generate electricity and simultaneously obtaining the high-selectivity value-added chemical ethylene.
In some embodiments, the solid state electrolyte material of the cogeneration fuel cell is BaZr0.1Ce0.7Y0.2O3-δThe cathode is a composite cathode, the composite cathode material is LSCF-SDC, wherein LSCF is La0.58Sr0.4Co0.2Fe0.8O3-δSDC is Sm0.2Ce0.8O1.9。
In some embodiments, the Ni-Co-Fe ternary nano-alloy particles have a particle size of 20 to 25 nm.
In some embodiments, there is also provided a method of making a cogeneration fuel cell anode, comprising the steps of:
dissolving lanthanum nitrate, strontium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate and ammonium molybdate in deionized water with nitric acid to form a mixed solution, then adding citric acid and EDTA as complexing agents, adjusting the pH value to be 7-8, then stirring for 2-4h, starting heating after full complexing until combustion is carried out, and preparing the porous material with the porous structureA perovskite precursor of the structure having the formula (La)0.6Sr0.4)0.95Fe0.7Co0.1Ni0.1Mo0.1O3-δ(ii) a Heating and reducing the perovskite matrix in a reducing atmosphere to prepare a symbiotic fuel cell anode material; mixing the anode material of the symbiotic fuel cell with polyethylene glycol, adding organic alcohol as a solvent, uniformly ball-milling for 6-12h, completely drying the organic alcohol, and uniformly grinding to obtain symbiotic fuel cell slurry; the intergrown fuel cell anode (LSFCNM anode) was made by screen printing the intergrown fuel cell slurry on the anode side of a solid electrolyte.
The perovskite precursor (LSFCNM) prepared in this example has the chemical formula of (La)0.6Sr0.4)0.95Fe0.7Co0.1Ni0.1Mo0.1O3-δBelonging to the ABO3A perovskite type oxide in which a site metal ion is in 12-coordination, B site metal ion is in 6-coordination, and O ion is also in 6-coordination. In the embodiment, the perovskite matrix material is subjected to reduction treatment, so that A-site defect treatment and B-site active transition metal ion Co-doping are performed on the LSFCNM perovskite structure, the structure and valence state balance of an anode is ensured, Ni-Co-Fe ternary alloy nanoparticles are precipitated in situ, the catalytic performance of the Ni-Co-Fe ternary alloy nanoparticles is effectively improved, and the Ni-Co-Fe ternary alloy nanoparticles can be used as a solid electrolyte supported SOFC (solid electrolyte Fuel cell) and can utilize ethane as fuel without CO2Discharging to generate electricity and simultaneously obtaining the high-selectivity value-added chemical ethylene.
In the embodiment, the symbiotic fuel cell anode has excellent stability in ethane catalytic reaction, and the uniformly dispersed Ni-Co-Fe ternary alloy nanoparticles provide more active sites, so that the adsorption and dissociation process of hydrocarbon fuel is facilitated, and the performance of the symbiotic fuel cell anode is better.
In some embodiments, the temperature of the calcination treatment is 900-1100 ℃, and the time of the calcination treatment is 4-6 h.
In some embodiments, the temperature of the heating reduction treatment is 800-850 ℃, and the time is 2-5 h. Under the reduction treatment condition, the surface of the perovskite matrix can be used for fully analyzing Ni-Co-Fe ternary alloy nanoparticles.
In some embodiments, the reducing atmosphere is primarily hydrogen or hydrogen argon, but is not limited thereto.
To verify the preparation of such perovskite oxide LSFCNM anodes, in some embodiments, to determine whether a pure phase structure was successfully prepared and to precipitate the phase structure of the ternary alloy in situ, the LSFCNM anodes required for the present invention were obtained, and XRD was used to characterize the samples before and after reduction of the LSFCNM electrode material, and the results are shown in fig. 2. The perovskite pure phase structure can be successfully obtained in the air atmosphere, and the precipitation diffraction peak of Ni-Co-Fe is found after reduction treatment, so that the generation of the alloy phase is verified.
In order to observe the changes of the micro-morphology and the like of the electrode material before and after reduction, fig. 3 shows the morphological characteristics of the LSFCNM powder before and after reduction. As can be seen by comparing SEM images of the powder before and after reduction, the surface of the material before reduction is smooth and porous, and the surface of the electrode after reduction has obvious existence of particles and is relatively uniform in distribution.
To determine the phase composition of the sample, the LSFCNM powder before and after reduction was further subjected to TEM analysis, as shown in fig. 4. The lattice spacing of the material before reduction corresponds to LaFeO3The (110) crystal plane of the phase (PDF # 74-2203). In the TEM image of the reduced powder, it can be seen that the nanoparticles having a particle size of about 20 to 25nm are uniformly dispersed on the surface of the perovskite substrate. To further determine the phase behavior of the nanoparticles and the matrix, interplanar spacings of the nanoparticles and the matrix were observed by HR-TEM analysis. The substrate interplanar spacing here corresponds to LaFeO3The (111) crystal plane of the phase (PDF #74-2203), indicating that the nanoparticles tend to be in LaFeO3The (111) crystal planes of the phases nucleate growth. The interplanar spacing of the precipitated nanoparticles was confirmed to be a ternary alloy. Therefore, through HR-TEM image analysis, Ni-Co-Fe nano alloy particles uniformly grow on the surface of the perovskite matrix, and the phenomena of agglomeration and coarsening of the anode metal catalyst on the matrix are effectively prevented when the battery runs at high temperature.
In some embodiments, the conductivity of the electrode material determines the electronic conductivity and the ionic conductivity of the electrode, so the magnitude of the conductivity has a very important role in the output performance of the battery. Here, the test was performed by a conventional conductivity measurement method, i.e., a direct current four-terminal method. Fig. 5 shows the electrical conductivity of LSFCNM oxide from 300 to 800 ℃ in a pure hydrogen atmosphere. It can be seen that the conductivity increases with increasing temperature, and that the increase in conductivity is found to be essentially a linear increasing trend with increasing temperature as the temperature increases above 500 ℃. The electron transport requirement of the anode material can be met by calculating the conductivity to obtain the corresponding conductivity activation energy of 0.530 eV.
In some specific examples, to understand the electrochemical process of LSFCNM anode in a hydrogen atmosphere, fig. 6 tested the electrochemical performance of the anode material in a symmetric cell. The test was carried out in a hydrogen atmosphere at a test temperature of from 600 to 800 ℃. Wherein the ohmic resistance RΩHas been eliminated, only for the polarization resistance RpAnd (6) carrying out analysis. The polarization impedances are calculated to be 1.026, 0.562, 0.329, 0.212 and 0.107 omega cm from 600 to 800℃ respectively2. The impedance test proves that the anode material has excellent electrochemical performance.
In some embodiments, the LSFCNM anode is used for the effect of an anode in a SOFC, and when used as an SOFC single cell anode, the SOFC single cell has a power density profile measured under hydrogen and ethane conditions as shown in fig. 7. As can be seen from FIG. 7, LSFCNM-BZCY/BZCY (300 μm)/LSCF-SDC single cell assembled by LSFN anode under hydrogen condition has maximum power density of 328mW.cm when operated at 750 deg.C-2And the highest power density of the battery under the ethane atmosphere is 258mW cm-2. Electrochemical oxidation of hydrogen is significantly more difficult due to the electrochemical oxidation of ethane as a cause of the degradation of cell performance in ethane. The anode material has excellent electrochemical performance in both hydrogen atmosphere and ethane atmosphere, and shows that the anode material has good catalytic activity and dehydrogenation capacity.
In some embodiments, LSFCNM was tested for long term cell stability when used as an anodeAnd (5) performing qualitative test. As shown in fig. 8. The specific implementation method comprises the following steps: at a working temperature of 750 ℃, an ethane flow rate of 30ml min-1The cell stability was evaluated by observing the change in current in a constant voltage mode of 0.6V in a reactor with LSFCNM/BZCY (300 μm)/LSCF-SDC cells. It can be seen that the discharge power of the battery is kept stable during the 30h test, which indicates that the anode material has very excellent anti-carbon stability and output power.
In some embodiments, the CO-free process is achieved by sequestering ethane and oxygen on both sides of the electrolyte, such that selective oxidative conversion of ethane to ethylene occurs on the anode side2The partial oxidation of ethane to the vent converts the endothermic process of ethane dehydrogenation to an exothermic oxidation reaction, as shown in fig. 9, the conversion of ethane, ethylene selectivity and calculated ethylene yield obtained using LSFCNM anode for solid oxide fuel cells using ethane in proton type conductors at an operating temperature of 650-. Importantly, at cell operation, the conversion of ethane is increased compared to open circuit voltage, while the selectivity to ethylene is hardly decreased. For example, at 750 ℃, the conversion rate of ethane is 41.6% under the open circuit state of the battery, and when the battery is subjected to constant current discharge, the conversion rate of ethane is improved to 43.6%, and simultaneously, the higher selectivity of ethylene is ensured. It can thus be shown that the consumption of hydrogen contributes to the dehydrogenation conversion of ethane.
In summary, the invention provides a symbiotic fuel cell anode and a preparation method and application thereof, wherein a citrate combustion method is adopted to prepare a pure-phase perovskite matrix, and then Ni-Co-Fe ternary alloy nanoparticles are precipitated in situ on the surface of the perovskite matrix through reduction treatment, wherein the chemical formula of the perovskite matrix material is (La)0.6Sr0.4)0.95Fe0.7Co0.1Ni0.1Mo0.1O3-δ. The invention provides a method for precipitating ternary alloy nano-particles on the surface of single perovskite in situ by manufacturing the defect of A site, doping multiphase active transition metal elements on the B site and precipitating the ternary alloy nano-particles on the surface of the single perovskite,the catalytic activity and the carbon deposition resistance of the anode to ethane are improved, the symbiosis of electric energy and added value products is realized, and the potential with great advantages is applied to the symbiotic type solid oxide fuel cell anode.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. The symbiotic fuel cell anode is characterized by comprising a perovskite matrix with a porous structure and Ni-Co-Fe ternary nano alloy particles which are subjected to reduction treatment and generated in situ on the surface of the perovskite matrix, wherein the perovskite matrix has a chemical formula of (La)0.6Sr0.4)0.95Fe0.7Co0.1Ni0.1Mo0.1O3-δ。
2. The anode for a symbiotic fuel cell according to claim 1, wherein the Ni-Co-Fe ternary nano-alloy particles have a particle size of 20-25 nm.
3. A method of making a symbiotic fuel cell anode comprising the steps of:
lanthanum nitrate, strontium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate and ammonium molybdate are dissolved in deionized water with nitric acid to form a mixed solution, then citric acid and EDTA are added as complexing agents, the pH value is adjusted to a preset value, combustion treatment is carried out after stirring, and the perovskite matrix with the porous structure is prepared, wherein the chemical formula of the perovskite matrix is (La)0.6Sr0.4)0.95Fe0.7Co0.1Ni0.1Mo0.1O3-δ；
Heating and reducing the perovskite matrix in a reducing atmosphere to prepare a symbiotic fuel cell anode material;
dissolving the symbiotic fuel cell anode material in an organic solvent to prepare symbiotic fuel cell slurry;
and preparing the intergrowth type fuel cell slurry into layers to obtain the intergrowth type fuel cell anode.
4. The production method for a symbiotic fuel cell anode according to claim 3, characterized in that the predetermined value is 7 to 8.
5. The method for preparing an anode of a symbiotic fuel cell according to claim 3, wherein the temperature of the calcination treatment is 900-1100 ℃, and the time of the calcination treatment is 4-6 h.
6. The method for preparing an anode of a symbiotic fuel cell according to claim 3, wherein the temperature of the heating reduction treatment is 800-850 ℃ and the time is 2-5 h.
7. The method of making a symbiotic fuel cell anode according to claim 3, wherein the reducing atmosphere is hydrogen or helium.
8. The method of making a symbiotic fuel cell anode according to claim 3, wherein the step of dissolving the symbiotic fuel cell anode material in an organic solvent to produce a symbiotic fuel cell slurry comprises:
mixing the anode material of the symbiotic fuel cell with polyethylene glycol, adding organic alcohol, carrying out ball milling for 6-12h, completely drying the organic alcohol, and uniformly grinding to obtain the symbiotic fuel cell slurry.
9. Use of a symbiotic fuel cell anode according to any one of claims 1 to 2 for the preparation of a symbiotic fuel cell.
10. Use of a symbiotic fuel cell anode according to claim 9, characterized in that the symbiotic fuel cell comprises a proton conductor electrolyte and a cathode and an anode respectively arranged on both sides of the solid electrolyte, the anode being the symbiotic fuel cell anode.
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