CN115020769A - Ethylene and electric energy symbiotic solid oxide fuel cell and preparation method thereof - Google Patents
Ethylene and electric energy symbiotic solid oxide fuel cell and preparation method thereof Download PDFInfo
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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Abstract
The invention discloses an ethylene and electric energy symbiotic solid oxide fuel cell and a preparation method thereof, wherein the ethylene and electric energy symbiotic solid oxide fuel cell comprises a solid electrolyte, an SFM perovskite structure anode and an SFM perovskite structure cathode which are positioned on two sides of the solid electrolyte, and the SFM perovskite structure anode comprises an SFM porous structure matrix and an SFM porous structureAnd the iron nanoparticles are distributed on the surface of the SFM porous structure matrix. The invention researches the excessive Fe doping of the B site of the SFM to obtain that the anode material has the best electrochemical performance when x is 0.075, and constructs the anode material with SF 1.575 M is taken as a fuel cell reactor of an anode, the symbiosis of ethylene and electric energy is successfully realized, and the fuel cell can reach 239.15mW cm at 750 DEG C ‑2 The conversion rate of ethane reached 31.08%. Meanwhile, the influence of Fe doping on the material structure is researched, and the precipitated nano particles can effectively promote the electrochemical performance of the electrode material and have better anti-carbon deposition stability when using hydrocarbon fuel.
Description
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to an ethylene and electric energy symbiotic solid oxide fuel cell and a preparation method thereof.
Background
Energy has become the basis upon which humans rely for survival and development. With the continuous development and progress of human society, the demand for energy is also increasing, and the exhaustion of fossil energy is an unchangeable fact. Ethylene is widely used as an important chemical raw material for synthesizing polymers such as polyethylene and the like, and is also used for synthesizing oxygen-containing compounds such as ethylene glycol and olefin derivatives, and the compounds have high application value and are generally used in the aspects of high molecules, medicine, chemical industry and the like. At present, ethylene mainly comes from the traditional steam cracking of petroleum and the technology for preparing ethylene by dehydrogenating alkane. Therefore, the development of efficient, clean and renewable energy technology is of great importance to the sustainable development of society.
Oxygen ion electrolyte solid oxide fuel cells (O-SOFCs) can convert the chemical energy of a fuel source directly into electrical energy, and where the anode is the site for fuel conversion, when ethane is used as an oxygen ion conductor SOFC fuel, it is critical to find an anode material that has good catalytic activity in ethane.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an ethylene and electric energy cogeneration type solid oxide fuel cell and a preparation method thereof, and aims to solve the problem that the performance of the fuel cell is poor due to low anode catalytic activity in the conventional solid oxide fuel cell.
The technical scheme of the invention is as follows:
the solid oxide fuel cell comprises a solid electrolyte, and an anode and a cathode which are positioned on two sides of the solid electrolyte and have an SFM perovskite structure, wherein the anode of the SFM perovskite structure comprises an SFM porous structure matrix and iron nanoparticles distributed on the surface of the SFM porous structure matrix.
The ethylene and electric energy symbiotic solid oxide fuel cell comprises an anode with an SFM perovskite structure and a cathode with an SFM perovskite structure, wherein the anode is made of Sr 2 Fe 1.5+x Mo 0.5 O 6-δ Wherein x is more than or equal to 0 and less than or equal to 0.1.
The ethylene and electric energy cogeneration type solid oxide fuel cell is characterized in that the material of the solid electrolyte is LSGM.
The ethylene and electric energy symbiotic solid oxide fuel cell comprises a cathode, wherein the cathode is a composite cathode, the composite cathode is made of LSCF-SDC, and LSCF is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ SDC is Sm 0.2 Ce 0.8 O 1.9 。
A preparation method of an ethylene and electric energy symbiotic type solid oxide fuel cell comprises the following steps:
providing an SFM perovskite structure anode, wherein the SFM perovskite structure anode comprises an SFM porous structure matrix and iron nanoparticles distributed on the surface of the SFM porous structure matrix;
and printing the anode and the cathode of the SFM perovskite structure on two sides of the solid electrolyte, and communicating the anode and the cathode of the SFM perovskite structure through a conducting wire to prepare the ethylene and electric energy symbiotic type solid oxide fuel cell.
The preparation method of the ethylene and electric energy symbiotic solid oxide fuel cell comprises the following steps:
providing a perovskite precursor material;
and (3) carrying out reduction treatment on the perovskite parent material in a reducing atmosphere, and growing iron nanoparticles on the surface of the SFM porous structure matrix to obtain the SFM perovskite structure anode.
The preparation method of the ethylene and electric energy symbiotic type solid oxide fuel cell comprises the step of carrying out reduction treatment on the perovskite parent material in a reducing atmosphere, wherein the temperature of the reduction treatment is 800-850 ℃, and the time is 2-5 h.
The preparation method of the ethylene and electric energy cogeneration type solid oxide fuel cell comprises the step of preparing a mixed gas of hydrogen and argon in a reducing atmosphere.
Has the advantages that: the solid oxide fuel cell provided by the invention comprises an anode with an SFM perovskite structure, and Fe nano particles are precipitated in situ on the SFM perovskite oxide by controlling the doping method of B-site Fe ions. The Fe ions are doped in a reducing atmosphere, so that Fe nanoparticles can be extracted from the host perovskite, the stable crystal structure and the precipitation of Fe nanoparticles with more active sites also enable the anode to have better catalytic activity and stability, and the SFM perovskite structure serving as the anode of the SOFC can realize the symbiosis of ethylene and electric energy by using ethane.
Drawings
FIG. 1 is SF 1.5+x The XRD pattern of the M sample after being calcined at 1100 ℃ for 3h under an air atmosphere.
FIG. 2 shows SF 1.5+x M samples in H 2 XRD pattern after reduction at 800 ℃ for 2h under Ar atmosphere.
In FIG. 3, a-c are SF 1.575 A line scanning curve graph of the M-R sample precipitated nanoparticles; d is F 1.575 The M-R sample gave rise to high-power TEM images of the nanoparticles.
FIG. 4 is SF 1.575 EDS analysis result chart of M-R sample.
FIG. 5 is 10% H at 50 ℃ -800 ℃ 2 SF in-Ar 1.5+x H of M (x ═ 0,0.025,0.05,0.075,0.1) sample 2 -a TPR map.
FIG. 6 is SF 1.5+x And (3) an XPS fitting result graph of the M-R sample, wherein a shows an XPS test total spectrum, b shows an XPS spectrum of an O element under different doping amounts, c shows a core level spectrum of Fe 2p, and d shows a core level spectrum of Mo 3 d.
FIG. 7 Shows (SF) 1.5+x M-LSGM-SF 1.5+x M) (x ═ 0,0.025,0.05,0.075,0.1) H at open circuit voltage 800 ℃ -600 ℃ for symmetrical cells 2 Impedance spectrum of the lower part.
FIG. 8 Shows (SF) 1.5+x M-LSGM-SF 1.5+x M) (x ═ 0,0.025,0.05,0.075,0.1) spectra were analyzed by fitting a symmetric cell to the relaxation time Distribution (DRT) method.
In FIG. 9 a is (SF) 1.5+x M-LSGM-SF 1.5+x M) (x ═ 0,0.025,0.05,0.075,0.1) H at 800 ℃ for symmetric cells 2 Impedance map of (1); b is (SF) 1.5+x M-LSGM-SF 1.5+x M) (x ═ 0,0.025,0.05,0.075,0.1) H at 800 ℃ for symmetric cells 2 DRT graph measured in (1).
FIG. 10 shows SF 1.5 M is the electrochemical performance result chart of the single cell of the anode in hydrogen and ethane.
FIG. 11 shows SF 1.575 M is the electrochemical performance result chart of the single cell of the anode in hydrogen and ethane.
FIG. 12, a is a graph showing results of ethane conversion at 650 deg.C-750 deg.C for open circuit and operating conditions of the fuel cell; b is the result chart of the ethylene selectivity of the fuel cell under the open circuit and working state at 650-750 ℃.
In FIG. 13, a is SF 1.575 M is used as a stability curve chart of a single cell of the anode under the constant voltage of 0.7V at 750 ℃; b and c are SEM topography images of the surface of the anode after the test.
Detailed Description
The present invention provides an ethylene and electric energy cogeneration type solid oxide fuel cell and a preparation method thereof, and the present invention is further described in detail below in order to make the purpose, technical scheme and effect of the present invention clearer and clearer. 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 invention provides an ethylene and electric energy symbiotic solid oxide fuel cell, which comprises a solid electrolyte, an anode with an SFM perovskite structure and a cathode, wherein the anode with the SFM perovskite structure and the cathode are positioned on two sides of the solid electrolyte, and the anode with the SFM perovskite structure comprises an SFM porous structure matrix and iron nanoparticles distributed on the surface of the SFM porous structure matrix.
In this embodiment, the material of the anode with SFM perovskite structure is Sr 2 Fe 1.5+x Mo 0.5 O 6-δ Wherein x is more than or equal to 0 and less than or equal to 0.1; the material of the solid electrolyte is LSGM; the cathode is a composite cathode, the composite cathode is made of LSCF-SDC, and LSCF is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ SDC is Sm 0.2 Ce 0.8 O 1.9 。
In some embodiments, there is also provided a method for manufacturing an ethylene and electric energy cogeneration type solid oxide fuel cell, comprising the steps of: providing an SFM perovskite structure anode, wherein the SFM perovskite structure anode comprises an SFM porous structure matrix and iron nanoparticles distributed on the surface of the SFM porous structure matrix; and printing the anode and the cathode of the SFM perovskite structure on two sides of the solid electrolyte, and communicating the anode and the cathode of the SFM perovskite structure through a conducting wire to prepare the ethylene and electric energy symbiotic type solid oxide fuel cell.
In this embodiment, the preparation of the SFM perovskite structure anode includes the steps of: providing a perovskite precursor material; and (3) carrying out reduction treatment on the perovskite parent material under the mixed gas of hydrogen and argon, wherein the temperature of the reduction treatment is 800-850 ℃, and the time is 2-5h, and growing iron nanoparticles on the surface of the SFM porous structure matrix to obtain the SFM perovskite structure anode.
The invention is further illustrated by the following specific examples:
perovskite matrix material Sr 2 Fe 1.5 Mo 0.5 O 6-δ (SFM) has a stable crystal structure, relatively high conductivity and excellent electrochemical properties, and the ions at a-and B-sites in the perovskite matrix material are more replaceable, which provides more possibilities for the choice of anode materials. Introducing catalytically active metal to B site to form solid solution oxide in air, reducing the active metal under reducing condition to precipitate from the oxide surface, and in-situ precipitatingThe nano-particles can improve the catalytic activity of the material and have stronger agglomeration resistance.
Example 1
Based on this, the invention uses Sr 2 Fe 1.5 Mo 0.5 O 6-δ As a matrix, a catalytic active metal Fe element is introduced into the B site, and nanoparticles are better precipitated by controlling the doping amount of the Fe element, so that the catalyst has better catalytic performance. The anode material is prepared by a citrate combustion method, and the preparation process comprises the following steps:
(1) sr (NO) according to a set stoichiometric ratio 3 ) 2 (≥99.5％)，Fe(NO 3 ) 3 ·9H 2 O (more than or equal to 99.99%) and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Dissolving O (more than or equal to 99.0%) in aqueous solution containing proper amount of nitric acid to make it completely dissolved;
(2) according to n (CA) :n (EDTA) :n (total ions) Sequentially adding Citric Acid (CA) and Ethylene Diamine Tetraacetic Acid (EDTA) into the solution according to the proportion of 1.5:1:1, and uniformly stirring;
(3) adding a proper amount of ammonia water, and adjusting the pH value of the solution to 7-7.5 to completely dissolve the EDTA;
(4) stirring for about 2h to fully form a metal complex solution, then keeping the temperature at 200 ℃, heating and evaporating to dryness until the solution is burnt, and collecting a precursor;
(5) and transferring the precursor into a crucible, and calcining at 1100 ℃ for 3h to obtain the prepared anode material powder.
Fe with different doping amounts is introduced according to the method to prepare powder Sr corresponding to the anode material 2 Fe 1.5+x Mo 0.5 O 6-δ (x ═ 0,0.025,0.05,0.075, and 0.1) and each is represented by SF 1.5 M、SF 1.525 M、SF 1.550 M、SF 1.575 M and SF 1.6 M; the anode material powder Sr 2 Fe 1.5+x Mo 0.5 O 6-δ X-ray diffraction (X ═ 0,0.025,0.05,0.075,0.1) as shown in fig. 1, it can be seen from fig. 1 that SrMoO appears under an oxidizing atmosphere when Fe is doped into the perovskite structure 4 The hetero peak of (1). However, when the powder is at 800 ℃ H 2 SrMoO was found after treatment for 2h under an-Ar atmosphere 4 The hetero peak of (a) disappears, and as shown in fig. 2, a single pure phase structure is obtained, and the stability of the structure is not deteriorated with the doping of Fe element, and a diffraction peak of Fe appears when 2 θ is 44.7 °. In order to confirm the deposition of Fe nanoparticles, TEM line scan analysis was performed on the reduced powder, and as shown in fig. 3 (a) to (d), it was found that the main component of the particles was Fe element. In order to further determine the phase characteristics of the nanoparticles and the matrix, the interplanar spacing of the nanoparticles and the matrix can be observed by performing high-power TEM analysis on the surface of the structure. The interplanar spacing of the substrates here is about 0.284nm, corresponding to SrFeO 3-x The (110) crystallographic plane of the phase (PDF #34-0638), indicating that the nanoparticles tend to be in SrFeO 3-x The (110) crystal planes of the phases nucleate growth. The interplanar spacing of the precipitated nanoparticles was about 0.201nm, which is substantially identical to the interplanar spacing of (110) in the Fe phase (PDF #87-0722, 0.20229nm) as determined by Jade spectroscopy. Therefore, through HR-TEM image analysis, Fe nanoparticles are desolventized in situ from the surface of the perovskite matrix, and the heterojunction structure anchored on the surface of the perovskite oxide to form the metal-metal oxide can effectively inhibit agglomeration, and is very important for improving the stability of the nano metal catalyst in the battery reaction process.
To confirm SF 1.575 Elemental analysis in M-R samples, TEM-EDS Mapping elemental analysis was performed, as shown in FIG. 4. From the point that the distribution of the particles on the surface of the material corresponds to the distribution of each element, the distribution of the Fe element can be seen from the figure to have several nanoclusters, which proves the existence of the Fe nanoparticles. And other Sr, Mo and O elements are uniformly distributed and correspond to the shape of the perovskite structure, and the phenomena of other large-particle agglomeration and the like do not occur. Indicating that the elements, except for the Fe nanoclusters, are uniformly dispersed in the perovskite structure.
Example 2
SF 1.5+x M electrocatalytic material H 2 TPR test
To evaluate the redox capacity of the catalyst, electrocatalytic materials were subjected to H 2 TPR test, the results are shown in FIG. 5, the test atmosphere is 10% H 2 Ar, the testing temperature range is 50-800 ℃. All samples had two low temperature reduction peaks in the low temperature range (300 ℃ C. -500 ℃ C.), which was attributed to Fe 4+ →Fe 3+ And Fe 3+ →Fe 2+ The valence state of (2). As the doping amount increased to 0.075, the position of the reduction peak shifted towards low temperature, indicating that the doping of Fe decreased the reduction temperature of the sample. While the area of the reduction peak is gradually reduced due to the gradual reduction of the consumption of hydrogen. The transformation of lattice oxygen to adsorbed oxygen occurs in a high temperature section (600-800 ℃), and Mo 6+ To Mo 5+ Thereby obtaining more oxygen vacancies. While Fe 4+ /Fe 3+ /Fe 2+ And Mo 6 + /Mo 5+ The existence of the redox couple promotes the transmission of ions on the surface of the anode, and effectively reduces the polarization impedance of the anode, thereby improving the catalytic capability of the electrode.
Example 3
SF 1.5+x Analysis of valence state and oxygen concentration of M electrocatalytic material metal element
To evaluate the oxygen vacancy concentration and study the valence evolution of the Fe and Mo elements, XPS spectra were recorded for the reduced samples at room temperature. FIG. 6 records the SF after reduction 1.5+x The XPS spectrum of the oxygen species of the M sample, shown in (a) of FIG. 6, shows the total spectrum of the XPS test, and it can be seen that the diffraction peaks of Fe, Mo and O elements are all the same as those in the literature [38] And the peak position correction of the test spectrogram is accurate. FIG. 6 (b) is an XPS spectrum of O element at different doping levels, with the distribution being determined by the lattice oxygen (O) lat. ) Adsorbing oxygen (O) ad. ) And OH - And (4) forming. By fitting the peaks of the oxygen species to analysis (see Table 1), the Fe doping increased the proportion of adsorbed oxygen compared to the undoped sample, which was maximized at a doping level of 0.075 compared to OH - The ratio of (c) is decreased. It is proved that the doping of Fe reduces the formation energy of oxygen vacancy and promotes the transformation of lattice oxygen to adsorbed oxygen, thereby promoting the electron migration channel of the anode in the SOFCs.
FIGS. 6 (c) and (d) show Fe 2p andmo 3d core level spectrum. By fitting XPS of all samples, Fe was observed to be present as a 4+/3+/2+ redox couple. The valence of Fe increased and then decreased with the increase of the doping amount, and the average valence of Fe was calculated from the value of x equal to 0 by valence transition analysis (Table 1) 3.04 Fe increased to 0.05 x 3.40 Then reduced to x-0.1 3.18 . Similarly, Mo in which the valence of Mo is 0 5.75 Mo when increasing to x 0.075 5.821 Mo after lowering x to 0.1 5.819 . Evidence of Fe 4+ /Fe 3+ ，Fe 3+ /Fe 2+ And Mo 6+ /Mo 5+ The existence of the redox couple provides more electron and ion transmission channels, and can remarkably promote the ion transmission and charge transfer process on the surface of the anode.
TABLE 1SF 1.5+x XPS analysis results of M-R samples
Example 4
SF 1.5+x Electrochemical impedance analysis of M electrocatalytic materials
To investigate the effect of Fe doping on SFM anode electrochemical performance, oxygen ion conductor LSGM electrolyte supported symmetric cells (SF) were operated at open circuit voltage 1.5+x M-LSGM-SF 1.5+x M) Electrochemical Impedance Spectroscopy (EIS) analysis was performed under a hydrogen atmosphere. Fig. 7 shows the ac impedance curve of a symmetrical cell at the corresponding temperature, with the ohmic impedance generated by the electrolyte subtracted for the purpose of comparing the polarization resistance of the electrodes, and the intercept of the low frequency band with the x-axis representing the polarization impedance of the electrodes. The impedances with different doping amounts are compared, and the comparison shows that when the addition amount of the Fe element is 0.075, the impedance is the minimum, which shows that the proper amount of Fe doping can effectively reduce the polarization resistance of the anode and promote the reaction process of the anode. Polarization resistance (R) P ) Mainly caused by adsorption and dissociation of gas, interface ion exchange and charge transfer reaction, and further reveals the kinetic effect of B-Fe doping on anode reactionIn response, the impedance spectrum was analyzed by the relaxation time Distribution (DRT) method, as shown in fig. 8. According to the DRT analysis, equivalent circuits (R2// CPE2) (R3// CPE3) (R4// CPE4) (R5// CPE5) were used to fit the results of the impedance spectra. Wherein R2 represents a high frequency arc (R) H ) R3 and R4 represent medium frequency arcs (R) M ) R5 represents a low frequency arc (R) L ) CPE2, CPE3, CPE4, CPE5 are constant phase elements. The high frequency band generally represents the ion transfer process at the three-phase interface of the electrolyte and the electrodes, the middle frequency band represents the charge transfer process, and the low frequency band is generally considered to be the process of gas diffusion and adsorption dissociation. It can be seen that the maximum DRT peak area in the low frequency band indicates that the low frequency band is the main control step of the material impedance, and when x is 0.075, the minimum peak area indicates that SF is present 1.575 M has the lowest polarization resistance and the best electrochemical activity.
For comparison of resistance change at the same temperature for different doping amounts, for SF 1.5+x The impedance spectrum of the M sample at 800 ℃ was compared by fitting analysis as shown in (a) of FIG. 9. The polarization resistance reached a minimum value when the doping amount x was 0.075. The area comparison of the DRTs also further confirms the comparison of the polarization impedances, as shown in fig. 9 (b).
By comparing SF 1.5 M and SF 1.575 And M is used as the anode and the discharge performance of the solid oxide fuel cell is improved. FIG. 10 is a chart with SF 1.5 Electrochemical performance of fuel cells with M as anode under hydrogen and ethane. In the whole test temperature interval, the open-circuit voltage is kept above 1.0V, which indicates that the battery has good sealing performance, no phenomena such as cracking and air leakage occur, and the test data has real contrast. Under hydrogen atmosphere, SF 1.5 M as the Peak Power Density (PPD) of the single cell of the anode reached 859.5, 479.05, 262.68 and 136.14mW · cm at 800 deg.C, 750 deg.C, 700 deg.C and 650 deg.C, respectively -2 . In the ethane atmosphere, the open circuit voltage slightly decreases with a decrease in temperature, which is because OCV of the cell is related to the partial pressure of oxygen across the cell, and when ethane is used as a fuel, the conversion rate of ethane decreases with a decrease in temperature, and therefore less hydrogen is generated at low temperatures, resulting in a smaller partial pressure across the cell, tableNow a relatively low OCV. The Peak Power Density (PPD) under ethane atmosphere reaches 128.2 mW.cm, 45.3 mW.cm and 14.6 mW.cm at 750 ℃, 700 ℃ and 650 ℃ respectively -2 . The significant performance degradation in ethane is due to the difficulty in electrochemical oxidation of hydrogen during the electrochemical oxidation of ethane. Impedance spectroscopy analysis at open circuit voltage revealed that the polarization impedance of the cell under ethane atmosphere was significantly greater than the impedance of the cell under hydrogen. For example, the polarization impedances in a hydrogen atmosphere and an ethane atmosphere at 750 ℃ are 0.583 and 4.452. omega. cm, respectively 2 It can be seen that the higher polarization resistance in the ethane atmosphere is the main reason for limiting the power density of the battery.
When using SF 1.575 With M as the anode, FIG. 11 records SF 1.575 Electrochemical performance of single cell with M as anode in hydrogen and ethane atmosphere, SF in hydrogen atmosphere 1.575 The Peak Power Density (PPD) of the single cell with M as the anode reached 1119.42, 623.81, 339.19 and 162.86mW · cm at 800 deg.C, 750 deg.C, 700 deg.C and 650 deg.C, respectively -2 . Peak Power Density (PPD) in ethane atmosphere reaches 239.15, 99.72 and 31.23mW cm at 750 deg.C, 700 deg.C and 650 deg.C respectively -2 . Compared with SF 1.5 M has very obvious promotion when being used as an anode and simultaneously has obvious promotion to SF 1.575 The polarization impedance of the cell was analyzed with M as the anode, and similarly, the polarization impedances in the hydrogen and ethane atmospheres were 0.299 and 0.637. omega. cm, respectively, using 750 ℃ as an example 2 Compared with SF 1.5 M as the anode, the polarization impedance is obviously reduced, so the power density is increased, and the catalytic activity of the electrode material is obviously improved.
Example 5
SF 1.5+x Analysis of SOFC reaction products with M Anode materials
Mixing SF 1.575 The anode product of M-LSGM-LSCF single cell operation in an ethane atmosphere was passed to a gas chromatography GC to test ethane conversion and ethylene selectivity, the results of which are shown in figure 12. From fig. 12 (a), it can be found that the conversion of ethane gradually increases with increasing temperature, and at 650 ℃ to 750 ℃, the conversion of ethane increases from 4.18% to 31.08%. In particular, when the battery is in operation, i.e. constantThe ethane conversion is increased in the current regime compared to the open circuit voltage. For example, at 750 ℃, the conversion of ethane when the cell is operated at OCV is 28.97%, whereas the conversion of ethane can be raised to 31.08% when the cell is in a constant current discharge operating state. The consumption of hydrogen during cell operation thus favors the dehydrogenation conversion of ethane. In FIG. 12 (b) shows the selectivity of ethylene at 650 deg.C-750 deg.C under the open-circuit and operating conditions of the fuel cell, it can be seen that the selectivity of ethylene decreases with increasing temperature, and at 650 deg.C-750 deg.C, the selectivity of ethylene decreases from 98.87% to 94.19%, which is attributed to the occurrence of side reactions at high temperature resulting in CH 4 、C 3 H 8 Etc., thereby decreasing the selectivity of ethylene. Compared with the traditional chemical reaction process, the output quantity of the ethylene of a single cell is higher, and the symbiosis of the ethylene with electric energy is effectively realized.
To further verify the stability of the fuel cell reactor, the trend of the current density of the single cell with time at 750 ℃ and a constant voltage of 0.7V was recorded in fig. 13 (a). No significant decay was found during the 7.5h test, indicating a stable battery output. At C 2 H 6 After a long-term test under the atmosphere, the anode surface was observed under magnification, as shown in (b) and (c) of FIG. 13, and SF can be seen 1.575 The surface of the M anode does not have obvious carbon deposition phenomenon, which shows that the cell material has good carbon deposition resistance stability and can be used for hydrocarbon fuel cells.
In conclusion, the SFM anode material is mainly subjected to B-site Fe doping, and Sr is prepared by using a citrate combustion method 2 Fe 1.5+x Mo 0.5 O 6-δ (SF 1.5+x M, x ═ 0,0.025,0.05,0.075, 0.1). The influence of doping amount on the electrode material structure and performance before and after doping is studied and successfully applied to the oxygen ion conduction type solid oxide fuel cell, and the following conclusion is obtained: by analyzing the phase of the material, when the doping amount x is less than or equal to 0.1, SF 1.5+x M has perovskite structure, a little impurity phase appears, reduction treatment is carried out on the material to find that the impurity phase disappears, and pure perovskite phase is formed and has brightObvious Fe phase is separated out; from the XPS analysis results, it is found that the average valence of Fe and Mo is reduced by doping Fe, the ionic radius is increased, and Fe 4+ /Fe 3+ ，Fe 3+ /Fe 2+ And Mo 6+ /Mo 5+ The existence of the redox couple provides more electron and ion transmission channels, and significantly promotes the ion transmission and charge transfer process on the surface of the anode; by construction with SF 1.5 M and SF 1.575 Compared with an oxygen ion electrolyte solid oxide fuel cell with M as an anode, the obtained Fe doping has an obvious effect on improving the electrochemical performance of materials, the Fe-Fe doped solid oxide fuel cell is successfully used in an ethane fuel cell to realize the symbiosis of ethylene and electric energy, and the fuel cell can reach 239.15 mW-cm at 750 DEG C -2 Ethane conversion reached 31.08%, furthermore, SF in a test of 7.5h 1.575 M shows better anti-carbon stability and electrocatalytic activity.
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 (8)
1. The solid oxide fuel cell is characterized by comprising a solid electrolyte, and an anode and a cathode which are positioned on two sides of the solid electrolyte and are in an SFM perovskite structure, wherein the anode in the SFM perovskite structure comprises an SFM porous structure matrix and iron nanoparticles distributed on the surface of the SFM porous structure matrix.
2. The co-generation type solid oxide fuel cell of ethylene and electric energy according to claim 1, wherein the material of the anode with SFM perovskite structure is Sr 2 Fe 1.5+x Mo 0.5 O 6-δ Wherein x is more than or equal to 0 and less than or equal to 0.1.
3. The co-generation type solid oxide fuel cell of ethylene and electric energy according to claim 1, wherein the material of the solid electrolyte is LSGM.
4. The co-generation solid oxide fuel cell of ethylene and electric energy according to claim 1, wherein the cathode is a composite cathode, and the material of the composite cathode is LSCF-SDC, wherein LSCF is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ SDC is Sm 0.2 Ce 0.8 O 1.9 。
5. A method for manufacturing an ethylene and electric energy cogeneration type solid oxide fuel cell according to claim 1, comprising the steps of:
providing an SFM perovskite structure anode, wherein the SFM perovskite structure anode comprises an SFM porous structure substrate and iron nanoparticles distributed on the surface of the SFM porous structure substrate;
and printing the anode and the cathode of the SFM perovskite structure on two sides of the solid electrolyte, and communicating the anode and the cathode of the SFM perovskite structure through a conducting wire to prepare the ethylene and electric energy symbiotic type solid oxide fuel cell.
6. The method for preparing an ethylene and electric energy cogeneration type solid oxide fuel cell according to claim 5, wherein the preparation of the SFM perovskite structure anode comprises the steps of:
providing a perovskite precursor material;
and (3) carrying out reduction treatment on the perovskite parent material in a reducing atmosphere, and growing iron nanoparticles on the surface of the SFM porous structure matrix to obtain the SFM perovskite structure anode.
7. The method for preparing an ethylene and electric energy cogeneration type solid oxide fuel cell as claimed in claim 6, wherein in the step of subjecting the perovskite precursor material to the reduction treatment in the reducing atmosphere, the temperature of the reduction treatment is 800-850 ℃ for 2-5 hours.
8. The method of manufacturing an ethylene and electric energy cogeneration type solid oxide fuel cell according to claim 6, wherein the reducing atmosphere is a mixed gas of hydrogen and argon.
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