Liquid Sb metal anode solid oxide fuel cell for olefin and power co-production

Abstract

The invention relates to the technical field of fuel cells. The invention discloses a solid oxide fuel cell with a liquid Sb metal anode, and particularly discloses a solid oxide fuel cell with a liquid Sb metal anode for co-production of olefin and electric power. The material of the anode of the solid oxide fuel cell comprises liquid Sb metal. According to the method, a liquid Sb metal anode is used for replacing a traditional Ni-YSZ anode. The solid oxide fuel cell using the liquid Sb metal anode has good propane fuel adaptability. Due to the density difference, the propane dehydrogenation byproduct-carbon deposit can be separated from the liquid Sb metal anode. And secondly, the liquid-solid contact surface between the anode and the electrolyte relieves the problem of carbon deposition and increases the oxidation reaction area of carbon deposition, so that the continuous operation of the battery is facilitated. Besides, dry propane is adopted for feeding, so that the stirring effect of gas on the liquid anode side is improved, carbon deposition separation, power generation product Sb2O3 transmission and carbon deposition oxidation reaction are accelerated, and the overall stability of the battery is further improved.

Description

Technical Field

[0001] This invention relates to a liquid Sb metal anode solid oxide fuel cell that integrates olefin production and power output, belonging to the field of fuel cell technology. Background Technology

[0002] Solid oxide fuel cells (SOFCs) offer the dual advantages of high energy conversion efficiency and environmental friendliness, directly converting the chemical energy stored in various fossil fuels into electrical energy, significantly reducing energy loss. Theoretically, any reducing gas can be used as fuel for SOFC operation. Currently, hydrogen is the mainstream SOFC fuel gas, but its production and transportation still face both economic and safety challenges. In contrast, propane (C3H8), with its unique physicochemical properties and mature market conditions, is considered one of the ideal fuels highly compatible with SOFC technology. Furthermore, when using propane as SOFC fuel, products such as propylene (C3H6), ethylene (C2H4), and hydrogen (H2) can be produced simultaneously. However, traditional SOFC anodes (nickel-yttrium stabilized zirconium oxide (Ni-YSZ)) face severe carbon buildup problems when using propane fuel, seriously affecting battery operation and equipment safety. Therefore, developing an anode that combines high propane compatibility and resistance to carbon buildup is crucial for the commercialization of SOFCs. Summary of the Invention

[0003] Purpose of the invention: The technical problem to be solved by the present invention is to address the shortcomings of the prior art by providing a liquid Sb metal anode solid oxide fuel cell for olefin and power cogeneration.

[0004] Inventive Concept: This invention proposes using a liquid Sb metal anode instead of the traditional Ni-YSZ anode. Solid oxide fuel cells using liquid Sb metal anodes exhibit good propane fuel compatibility. Due to density differences, propane dehydrogenation byproducts—carbon deposits—can be separated from the liquid Sb metal anode. Secondly, the liquid-solid contact area between the anode and carbon deposits mitigates carbon deposition and increases the carbon deposit oxidation reaction area, thus facilitating continuous battery operation. Furthermore, using dry propane feed increases the gas stirring effect on the liquid anode side, accelerating carbon deposit separation, the transport of Sb₂O₃ (the power generation product), and the carbon deposit oxidation reaction, thereby improving the overall stability of the battery.

[0005] To solve the above-mentioned technical problems, the present invention discloses the following technical solution:

[0006] Application of a solid oxide fuel cell in the co-production of olefins and electricity from propane.

[0007] In some embodiments, the solid oxide fuel cell includes an electrolyte plate and an anode and a cathode located on opposite sides of the electrolyte plate; the anode is made of liquid Sb metal, and the cathode is made of Ba. 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Where δ represents the oxygen vacancy content; the material of the electrolyte plate includes Ce. 0.8 Gd 0.2 O 1.9 .

[0008] In some embodiments, the anode and cathode are disposed on opposite sides of an electrolyte plate and connected by a current collector. In some embodiments, the current collector for the anode is a Re line, and the current collector for the cathode is an Ag line.

[0009] In this invention, the cathode contains Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ The cathode electrode material is prepared by the sol-gel method. In some embodiments, the sol-gel method includes: mixing and dissolving Ba(NO3)2, Sr(NO3)2, Co(NO3)2·6H2O and Fe(NO3)3·9H2O, then adding ethylenediaminetetraacetic acid, citric acid monohydrate and ammonia water to form a complex, and drying and calcining the mixed solution when it becomes gel-like to obtain the cathode electrode material. In some embodiments, the molar ratio of Ba(NO3)2, Sr(NO3)2, Co(NO3)2·6H2O, and Fe(NO3)3·9H2O is 5:5:8:2; in some embodiments, the mass-to-volume ratio of ethylenediaminetetraacetic acid (EDTA) to ammonia is 0.30-0.42 g / mL, and the mass-to-volume ratio of citric acid monohydrate to ammonia is 0.47-0.57 g / mL; in some embodiments, the mixing and dissolving is performed in water; in some embodiments, the concentration of ammonia is 20%-30%, such as 25%; in some embodiments, after mixing and dissolving Ba(NO3)2, Sr(NO3)2, Co(NO3)2·6H2O, and Fe(NO3)3·9H2O, the mixture is first heated to 75-85 °C, and then EDTA, citric acid monohydrate, and ammonia are added for complexation; in some embodiments, the drying and calcination is performed at 170-190 °C for 8-12 hours. The precursor is obtained by calcining at 900-1100℃ for 4-6 h; in some embodiments, the drying temperature is 180℃; in some embodiments, the calcination temperature is 1000℃; in some embodiments, the calcination time is 5 h.

[0010] In this invention, the electrolyte plate is prepared by a dry pressing method. In some embodiments, the dry pressing method includes: dry pressing and calcining GDC powder, i.e., first physically pressing and shaping, then calcining to obtain the electrolyte. In some embodiments, the physical pressing pressure is 1.0-1.5 MPa. In some embodiments, the calcination is carried out at 1250-1450 °C for 4-6 h; in some embodiments, the calcination temperature is 1350 °C; in some embodiments, the calcination time is 5 h. In some embodiments, a crude electrolyte is obtained after calcination, and the crude electrolyte is wet-milled to 0.2-0.4 mm using sandpaper and ethanol.

[0011] The solid oxide fuel cell described in this invention is manufactured by the following method: Ba-containing... 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ The cathode paste is sprayed onto one side of the electrolyte plate, calcined, and sealed to one end of a ceramic tube. Sb powder is added to the ceramic tube and heated to form a liquid metal anode, Sb. In some embodiments, the heating is performed from room temperature to 750-850 °C at a rate of 0.5-2 °C / min. -1 In some embodiments, the heating process parameters are: heating from room temperature to 800 °C at a rate of 1 °C / min. -1 In some embodiments, the ceramic tube has an inner diameter of 8-10 mm, an outer diameter of 11-13 mm, and a length of 33-37 cm.

[0012] The technical solution provided by this invention uses GDC electrolyte support, liquid metal Sb as the anode, and Ba... 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Using gaseous dry propane as the cathode, a stable co-production of olefins and electricity is achieved by feeding gaseous dry propane into the resulting solid oxide fuel cell. In some embodiments, propane fuel is introduced into the interior of the liquid Sb metal anode through a quartz inlet pipe. In some embodiments, the dimensions of the quartz inlet pipe are: inner diameter 3-5 mm, outer diameter 5-7 mm, and length 42-44 cm. In some embodiments, the dimensions of the quartz tube are: inner diameter 4 mm, outer diameter 6 mm, and length 43 cm.

[0013] In this invention, unless otherwise specified, the olefins referred to are a collective term for mixed olefins of ethylene and propylene, C. n H 2n .

[0014] In the solid oxide fuel cell provided by this invention, on the one hand, the excellent oxygen ion conductivity of the GDC electrolyte is beneficial to the oxidation of the liquid Sb anode, thereby accelerating the carbon deposition oxidation reaction and propane dehydrogenation reaction of the cell. On the other hand, the propane dehydrogenation reaction is a reaction with an increasing number of gases. Compared with solid carbon feed solid oxide fuel cells using liquid Sb metal anodes, the gaseous products generated by dry propane feed increase the gaseous agitation of the liquid Sb metal anode. Gas agitation not only facilitates the transport rate of the power generation product Sb₂O₃ and the dehydrogenation byproduct—carbon deposits—from the inside of the anode to the anode surface, thus ensuring stable power output, but also accelerates the reaction area between the dehydrogenation byproducts—carbon deposits—and the power generation product Sb₂O₃, thereby accelerating the carbon deposit treatment efficiency. X-ray diffraction (XRD) and Raman spectroscopy analyses have shown that the liquid Sb metal anode can keep carbon deposits away from the anode / electrolyte contact area, which is beneficial to the long-term stable operation of the cell. On the one hand, the pyrolysis byproduct - carbon deposits - can be oxidized by the power generation product Sb2O3, thereby increasing the value of the carbon deposits into electricity and improving the overall economic efficiency of the system.

[0015] Beneficial effects:

[0016] This invention employs a GDC electrolyte support and a liquid Sb metal anode solid oxide fuel cell (SOCFC) composed of a liquid Sb metal anode and a BSCF cathode. Propane fuel catalytic and electrochemical tests on the liquid Sb metal anode SOCFC revealed good propane fuel compatibility, indicating that the fuel cell can be used for both olefin and electricity dual-output applications.

[0017] The single battery provided by this invention achieves a power output of 274 mW cm⁻¹ using propane as fuel at 800 °C, 750 °C, 700 °C, and 650 °C, respectively. -2 215 mW cm -2 162 mW cm -2 73 mW cm -2 At 750 °C, the propane conversion rate reached 86%, and the olefin yield reached 51.5%. The stability test duration of the propane-fueled battery was as long as 16.7 h, far exceeding the stability test duration of the traditional Ni-YSZ anode solid oxide fuel cell with propane as fuel (10.12 min), demonstrating its potential in gas-power cogeneration. Attached Figure Description

[0018] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the present invention in the above and / or other aspects will become clearer.

[0019] Figure 1These are the XRD patterns of the BSCF cathode material and the electrolyte material GDC.

[0020] Figure 2 XRD patterns of the fuel cell anode surface after continuous power generation with different inlet gases (Ar and C3H8), and Raman patterns of the surface and interior of a single-cell anode after power generation with C3H8 supply. During power generation, the cell temperature was maintained at 750 °C and the cell power density was maintained at 100 mW / cm³. -2 about.

[0021] Figure 3 The scanning electron microscope (SEM) characterization and electron capability dispersion (EDS) elemental analysis spectra of the anode surface and interior of the single cell after power generation under C3H8 supply are obtained.

[0022] Figure 4 It includes the IV curves and corresponding IP curves of a single cell at different temperatures, as well as its impedance spectrum and SEM image of the single cell cross-section.

[0023] Figure 5 This is a comparison chart of power density, polarization impedance, ohmic impedance, and OCV when the anode supply gas of a single cell is Ar and C3H8.

[0024] Figure 6 The temperature is 650~800℃, and the propane inlet gas flow rate is 20 mL / min. -1 At that time, the conversion rate of propane, the selectivity of propylene, and the C n H 2n Graph showing yield as a function of temperature.

[0025] Figure 7 Stability tests were conducted on solid oxide fuel cells with liquid Sb metal anodes and solid oxide fuel cells with conventional Ni-YSZ anodes under continuous propane supply.

[0026] Figure 8 This is a diagram of the equipment layout for testing a solid oxide fuel cell with a liquid Sb metal anode.

[0027] Figure 9 The reaction mechanism diagram, propane conversion rate, and olefin selectivity of the single cell provided by this invention at 750 °C are shown. Detailed Implementation

[0028] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.

[0029] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0030] This invention relates to a solid oxide fuel cell with a liquid Sb metal anode supported by a GDC electrolyte, wherein the cathode perovskite material has the molecular formula Ba. 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF), where δ represents the oxygen vacancy content, and its electrolyte formula is Ce. 0.8 Gd 0.2 O 1.9 This solid oxide fuel cell (SOCF) uses liquid metal Sb as its anode and pure, dry propane as its inlet gas. Catalytic and electrochemical tests on the liquid Sb metal anode SOCF revealed good propane fuel compatibility, indicating its capability for dual olefin-electricity output. XRD analysis of the anode surface composition after different inlet gas levels confirmed Sb₂O₃ as the power generation product. Characterization of different anode regions after power generation using SEM combined with Raman spectroscopy demonstrated the self-separation properties of carbon deposits. Electrochemical impedance spectroscopy (EIS) showed low polarization resistance. The polarization resistances of a single cell at 800, 750, 700, and 650 °C were 0.047, 0.071, 0.142, and 0.715 Ω cm⁻¹, respectively. 2 At 750 °C, the propane conversion rate reached 86%, and the olefin yield reached 51.5%. Finally, the single-cell performance of the liquid Sb metal anode solid oxide fuel cell was tested, and the results showed that the output power using propane as fuel reached 274 mW / cm² at 800 °C, 750 °C, 700 °C, and 650 °C, respectively. -2 215mW cm -2 162 mW cm -2 73 mW cm -2 The output power at each temperature point was slightly higher than that when argon was used as the anode feed gas. This indicates that the addition of propane increased the stirring efficiency within the liquid Sb anode, promoted the transport of the power generation product Sb₂O₃ to the anode surface, and thus contributed to the increase in battery output power. Furthermore, the battery exhibited excellent performance stability, with a stability test duration of 16.7 h using propane as fuel, far exceeding the stability test duration (10.12 min) of traditional Ni-YSZ anode solid oxide fuel cells using propane as fuel.

[0031] Example 1: Preparation of perovskite BSCF cathode and electrolyte plate GDC

[0032] This embodiment provides a solid oxide fuel cell cathode Ba with a liquid Sb metal anode. 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF) and electrolyte plate Ce 0.8 Gd 0.2 O 1.9 The preparation method and specific steps are as follows:

[0033] (1) Cathode: Weigh 6.533 g of barium nitrate, 5.291 g of strontium nitrate, 11.641 g of cobalt nitrate hexahydrate, and 4.04 g of ferric nitrate nonahydrate, add them to a beaker, and then add deionized water to dissolve them to obtain a mixed solution. Weigh 29.224 g of ethylenediaminetetraacetic acid and 42.028 g of citric acid monohydrate, and dissolve them in 80 mL of GR 25% (Shanghai Test) ammonia water to prepare a complexing agent.

[0034] The mixed solution was heated and stirred on a magnetically controlled stirring table at 80 °C. Then, a complexing agent was added to the mixed solution for complexation. Once the mixed solution reached a gel-like consistency, it was dried in a 180 °C oven for 8 hours to obtain BSCF precursor powder. This precursor powder was then calcined in a muffle furnace at 1000 °C for 5 hours. After cooling, the calcined powder was ground into a fine powder in an agate mortar to finally obtain the BSCF perovskite cathode material.

[0035] (2) Electrolyte plate: Weigh 0.35 g of commercial GDC powder from Fuel Cell, add the powder into a 12 mm diameter circular tableting mold and vibrate until the surface is smooth. Then place the mold under a tablet press and apply physical pressure of 1.0-1.5 MPa for 2 minutes. Remove the GDC electrolyte plate. Coat the obtained GDC plate with Al2O3 powder and place it on an Al2O3 plate. Then calcine these GDC plates in a muffle furnace at 1350 °C for 5 hours to obtain a rough electrolyte plate. Wet the rough electrolyte plate with 800-mesh sandpaper and ethanol to 0.3 mm, and then ultrasonically wash it with ethanol to obtain the electrolyte plate.

[0036] Example 2 Half-cell preparation

[0037] Weigh 1 g of the cathode powder BSCF prepared in Example 1, 10 ml of isopropanol, 2 ml of ethylene glycol, and 0.8 ml of glycerol and pour them into a high-energy ball mill. After ball milling at 400 rpm for 30 min, transfer the slurry to a culture bottle using a dropper to obtain the desired cathode slurry. Place the prepared GDC electrolyte plate on a heating table and preheat it at 150 °C. Using a spray gun, under nitrogen pressure, evenly spray the prepared cathode slurry onto one side of the electrolyte plate. After the liquid has completely evaporated, place the sprayed electrolyte in a high-temperature muffle furnace and calcine it at 1000 °C for 2 h to obtain a GDC plate with a BSCF cathode. Note that the heating and cooling rates are both 5 °C / min. -1 This ensures a tight connection between the oxygen electrode material and the electrolyte material. An Ag wire is connected to one side of the GDC plate with the BSCF cathode for current collection, resulting in the final half-cell.

[0038] Example 3: Preparation of a single cell

[0039] Seal one end of the prepared half-cell with ceramic adhesive, ensuring the side with the BSCF cathode faces outwards. Add 5 grams of Sb powder to the other end of the ceramic tube, then insert a Re wire as a current collector into the Sb powder. Place the ceramic tube containing the half-cell in a tube furnace and heat it to 800 °C at a rate of 1 °C / min. -1 Ceramic tube dimensions: inner diameter 9 mm, outer diameter 12 mm, length 35 cm.

[0040] Comparative Examples

[0041] A conventional Ni-YSZ anode solid oxide fuel cell was fabricated, with BSCF as the cathode, YSZ as the electrolyte, and GDC as the barrier layer. Following the preparation method in Example 2, BSCF cathode slurry was sprayed onto the GDC barrier layer, YSZ electrolyte, and Ni-YSZ half-cell, and then sintered to obtain the conventional Ni-YSZ anode solid oxide fuel cell. During the test preparation phase, 50 ml / min was continuously introduced into the anode side. -1 Hydrogen gas is used as a protective gas.

[0042] Characterization results

[0043] (1) X-ray diffraction (XRD) characterization of cathode materials and electrolyte materials

[0044] like Figure 1 The image shows the refined XRD patterns of the BSCF cathode material and the GDC electrolyte material. We can see that both BSCF and GDC possess good crystal structures and no obvious impurity phases were found. The space group of BSCF is Pm-3m, and the space group of GDC is Fm-3m.

[0045] (2) 20 mL of the solution was introduced into the anode side of each single cell. -1 The experiment and characterization of Ar or C3H8 and continuous power generation were conducted. During this process, the battery temperature was stabilized at 750 °C and the power density was stabilized at 100 mW / cm³. -2 about.

[0046] like Figure 8 As shown, the intake of Ar or C3H8 is controlled by a pressure reducing valve, the intake flow rate is controlled by a flow meter, and the battery power density is controlled by a load.

[0047] (a) X-ray diffraction (XRD) characterization

[0048] like Figure 2 As shown in Figure a, when the anode supply gas is Ar, after fuel cell power generation testing, the anode surface material is Sb₂O₃, proving that the power generation product is Sb₂O₃. When the anode supply gas is C₃H₈, the anode surface material is Sb, proving that the power generation product Sb₂O₃ is consumed by C₃H₈ and its dehydrogenation products.

[0049] (b) Raman characterization

[0050] Figure 2 b shows the Raman spectra of the anode surface and interior of the single cell after power generation under C3H8 supply. The results show that the Raman spectrum at the anode surface is highest at 1351 cm⁻¹. -1 and 1594 cm -1 Characteristic peaks (D and G peaks) of carbon deposition were observed at the anode surface, with a D / G ratio of 0.775. However, no obvious D and G peaks were detected in the Raman spectrum inside the anode. These results confirm that, due to density differences, carbon deposition is mainly concentrated on the anode surface.

[0051] (c) Electron microscopy characterization

[0052] Scanning electron microscopy (SEM) was used to characterize the surface and interior of the anode of the single cell after power generation under C3H8 supply, and electronic capability dispersion (EDS) elemental analysis was performed on the anode surface and interior. Figure 3 As shown in ab. SEM results show the anode surface ( Figure 3 a) Rough, with filamentous material present, while the interior ( Figure 3 b) Maintain a smooth surface. EDS results show that the C signal is more pronounced on the filamentous material, confirming that the filamentous material on the anode surface is the morphology of carbon deposits, a byproduct of dehydrogenation. EDS results inside the anode show that it mainly displays the signal of Sb, therefore the main component inside the anode is metallic Sb.

[0053] (3) Single-cell electrochemical testing

[0054] Experimental procedure: Electrochemical and catalytic tests were conducted within the temperature range of 650-800 °C. The test parameters were measured in 20 mL / min increments. -1 C3H8 is introduced into the anode of the single cell at a flow rate of [missing information].

[0055] (a) Single cell output power and battery impedance Figure 4 Figure a shows the IV curves and corresponding IP curves of a single cell at different temperatures. In the experiment, 20 mL / min... −1 C3H8 was introduced into the anode at a flow rate of [missing information]. At 800, 750, 700, and 650 °C, the peak power density of the single cell reached 274 mW / cm². -2 215 mW cm -2 162 mW cm -2 73 mW cm -2 The corresponding OCV values ​​are 0.69, 0.72, 0.74 and 0.77 V, respectively. Figure 4 b shows the impedance spectra of the single cell tested in the temperature range of 650–800 °C. The polarization impedances of the single cell at 800, 750, 700, and 650 °C are 0.047, 0.071, 0.142, and 0.715 Ω cm, respectively. 2 The corresponding ohmic impedances are 0.40, 0.51, 0.69, and 1.33 Ω cm, respectively. 2 At each temperature point, the ohmic impedance accounted for more than 65% of the total impedance, indicating that the battery performance was mainly controlled by the ohmic impedance.

[0056] Figure 4 c is a cross-sectional view of the battery, showing that the BSCF cathode thickness is 4µm. Figure 5 Figures ac show a comparison of single-cell power density, polarization impedance, and ohmic impedance when the anode supply gas is Ar and C3H8, respectively. The results show that the single-cell power density is higher when the supply gas is C3H8 than when the supply gas is Ar. However, both the polarization impedance and ohmic impedance are lower when the supply gas is Ar. This demonstrates that when the supply gas is C3H8, C3H8 and its dehydrogenation products can effectively convert to Sb2O3, thus reducing the battery's ohmic impedance. Furthermore, when C3H8 is introduced into the anode, the C3H8 dehydrogenation reaction is a reaction with an increased number of gases. Compared to introducing Ar into the anode, the gaseous products generated by the C3H8 feed promote the stirring effect inside the liquid Sb metal anode, thereby accelerating the transport and reaction rate of the power generation product Sb2O3 and the dehydrogenation byproduct—carbon deposits—within the anode, resulting in a decrease in the battery's polarization impedance. The reduction in polarization impedance and ohmic impedance synergistically promotes the improvement of battery performance. Figure 5Figure d shows the comparison of the OCV of a single cell when the anode supply gas is Ar and C3H8. The results show that Ar and C3H8 do not affect the OCV of the single cell, proving that the cell OCV is determined by the Sb oxidation reaction (2Sb + 3O). 2- The control of →Sb2O3 also indicates that liquid metal Sb has the dual function of acting as an anode and fuel.

[0057] (b) Propane dehydrogenation performance

[0058] Figure 6 a shows the relationship between propane conversion and propylene selectivity in liquid Sb as a function of temperature. The results indicate that at 650–800 °C, a propane inlet gas flow rate of 20 mL / min is suitable. -1 At that time, the conversion rates of propane were 24.5%, 59.3%, 86.0% and 98.5%, respectively, and the selectivity of propylene were 37.1%, 24.7%, 16.4% and 5.6%, respectively. Figure 6 b shows the relationship between propane conversion and olefin yield in liquid Sb as a function of temperature. The results indicate that, within the range of 650–800 °C, a propane inlet gas flow rate of 20 mL / min is optimal. -1 At that time, C n H 2n The yields were 18.9%, 36.0%, 51.5%, and 50.2%, respectively. Figure 6 c shows the percentage of each component in the anode outlet gas at each temperature point. The results indicate that the main gaseous products of propane dehydrogenation are propylene, ethylene, and hydrogen. The main byproducts are methane and ethane.

[0059] (c) Stability

[0060] Figure 7 A stability test of a solid oxide fuel cell with a liquid Sb metal anode under continuous propane supply was shown. The results showed that a single cell could discharge continuously for 16.7 hours. This operating time significantly exceeds the stability test duration of a conventional Ni-YSZ anode solid oxide fuel cell under continuous propane supply. Figure 7 (b, 10.12 minutes). The results show that the solid oxide fuel cell with liquid Sb metal anode has good propane compatibility and performance output stability.

[0061] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. The use of a solid oxide fuel cell in the co-production of olefins and electricity from propane, characterized in that, The solid oxide fuel cell includes an electrolyte plate and an anode and a cathode located on both sides of the electrolyte plate; the anode is made of liquid Sb metal, and the cathode is made of Ba. 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ , where δ is the oxygen vacancy content.

2. The application according to claim 1, characterized in that, The electrolyte plate is made of Ce. 0.8 Gd 0.2 O 1.9 .

3. The application according to claim 1, characterized in that, The anode and cathode are disposed on both sides of the electrolyte plate and are connected by a collector line.

4. The application according to claim 3, characterized in that, The current collector of the anode is a Re line, and the current collector of the cathode is an Ag line.

5. The application according to claim 1, characterized in that, Ba in the cathode 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ It was prepared by the sol-gel method.

6. The application according to claim 5, characterized in that, The sol-gel method includes: mixing and dissolving Ba(NO3)2, Sr(NO3)2, Co(NO3)2·6H2O and Fe(NO3)3·9H2O, then adding ethylenediaminetetraacetic acid, citric acid monohydrate and ammonia water to complex the mixture, and drying and calcining the mixture when it becomes gel-like to obtain the cathode electrode material. Optionally, the drying and calcination are carried out by drying at 170-190 °C for 8-12 h to obtain the precursor, and the obtained precursor is calcined at 900-1100 °C for 4-6 h.

7. The application according to claim 1, characterized in that, The electrolyte plate is prepared by dry pressing.

8. The application according to claim 7, characterized in that, The dry pressing method includes: physically pressing GDC powder into shape, and then calcining it to obtain an electrolyte; optionally, the physical pressing pressure is 1.0-1.5 MPa; optionally, the calcination is carried out at 1250-1450 °C for 4-6 h.

9. The application according to claim 1, characterized in that, The anode is obtained by directly heating metal powder.

10. The application according to claim 1, characterized in that, The solid oxide fuel cell is manufactured by the following method: Ba-containing... 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ The cathode paste is sprayed onto one side of the electrolyte plate, calcined, and sealed to one end of a ceramic tube. Sb powder is added to the ceramic tube and heated to form a liquid metal anode, Sb. Optionally, the heating is performed from room temperature to 750-850 °C at a rate of 0.5-2 °C / min. -1 .

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