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CN-121983586-A - Liquid Sb metal anode solid oxide fuel cell for co-production of olefin and power

CN121983586ACN 121983586 ACN121983586 ACN 121983586ACN-121983586-A

Abstract

The invention relates to the technical field of fuel cells. In particular discloses a liquid Sb metal anode solid oxide fuel cell used for the co-production of olefin and power, the anode material of the solid oxide fuel cell comprises liquid Sb metal. The invention proposes to use a liquid Sb metal anode instead of the conventional Ni-YSZ anode. Solid oxide fuel cells using liquid Sb metal anodes have good propane fuel suitability. Due to the density difference, the propane dehydrogenation byproduct, carbon deposition, can be separated from the liquid Sb metal anode. Secondly, the liquid-solid contact surface between the anode and the electrolyte relieves the problem of carbon deposition, increases the carbon deposition oxidation reaction area, and is favorable for continuous operation of the battery. In addition, the stirring effect of gas on the liquid anode side is increased by adopting dry propane feeding, carbon deposition separation is accelerated, the power generation product Sb 2 O 3 is transported, and carbon deposition oxidation reaction is carried out, so that the overall stability of the battery is improved.

Inventors

  • ZHOU WEI
  • LIU WENXIN
  • JIA KAI
  • LI YONGXIN
  • LI WENHUAI

Assignees

  • 南京工业大学

Dates

Publication Date
20260505
Application Date
20260212

Claims (10)

  1. 1. The application of the solid oxide fuel cell in co-production of olefin and electric power by taking propane as a raw material is characterized in that the solid oxide fuel cell comprises an electrolyte plate, and an anode and a cathode which are positioned on two sides of the electrolyte plate, wherein the material of the anode comprises liquid Sb metal, and the material of the cathode comprises Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ , wherein delta is oxygen vacancy content.
  2. 2. The use of claim 1, wherein the material of the electrolyte sheet comprises Ce 0.8 Gd 0.2 O 1.9 .
  3. 3. The use according to claim 1, wherein the anode and cathode are arranged on both sides of an electrolyte plate and are connected by a collector line.
  4. 4. Use according to claim 3, characterized in that the current collector of the anode is Re wire and the current collector of the cathode is Ag wire.
  5. 5. The use according to claim 1, wherein Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ in the cathode is prepared by sol-gel method.
  6. 6. The method according to claim 5, wherein the sol-gel method comprises mixing and dissolving Ba (NO 3 ) 2 、Sr(NO 3 ) 2 、Co(NO 3 ) 2 ·6H 2 O and Fe (NO 3 ) 3 ·9H 2 O), adding ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water for complexing, and drying and calcining when the mixed solution is gelatinous to obtain the cathode electrode material; Optionally, the drying and calcining are performed at 170-190 ℃ to obtain a precursor by drying 8-12 h, and the obtained precursor is calcined at 900-1100 ℃ to obtain 4-6 h.
  7. 7. The use according to claim 1, wherein the electrolyte sheet is prepared by dry pressing.
  8. 8. The use according to claim 7, wherein the dry pressing method comprises forming the GDC powder by physical pressing and calcining to obtain an electrolyte, optionally the physical pressing is performed at a pressure of 1.0-1.5 MPa, optionally the calcining is performed at 1250-1450 ℃ for 4-6 h.
  9. 9. The use according to claim 1, wherein the anode is obtained by direct heating of a metal powder.
  10. 10. The use according to claim 1, wherein the solid oxide fuel cell is manufactured by spraying a cathode slurry containing Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ on one side of an electrolyte plate, calcining and sealing the cathode slurry on one end of a ceramic tube, adding Sb powder to the ceramic tube, heating to form a liquid metal anode Sb, optionally heating from room temperature to 750-850 ℃, and heating at a rate of 0.5-2 ℃ min -1 .

Description

Liquid Sb metal anode solid oxide fuel cell for co-production of olefin and power Technical Field The invention relates to a liquid Sb metal anode solid oxide fuel cell integrating olefin production and power output, belonging to the technical field of fuel cells. Background Solid Oxide Fuel Cells (SOFCs) have the dual advantages of efficient energy conversion and environmental friendliness and can directly convert chemical energy stored in a variety of fossil fuels to electrical energy, significantly reducing energy losses. In theory, any reducing gas can be supplied as fuel to the SOFC operation. Currently, the main SOFC fuel gas is hydrogen, and the preparation and transportation of hydrogen still face economic and safety challenges. In contrast, propane (C 3H8), by virtue of its unique physicochemical properties and mature market conditions, is considered to be one of the ideal fuels highly compatible with SOFC technology, and when propane fuel is used as SOFC fuel gas, products such as propylene (C 3H6), ethylene (C 2H4), hydrogen (H 2) and the like can be produced simultaneously. However, conventional SOFC anodes (nickel-yttrium stabilized zirconia (Ni-YSZ)) face severe carbon deposition problems with propane fuel, severely affecting cell operation and equipment safety. Therefore, the development of an anode with both high-adaptation propane and carbon deposition tolerance is a key to promote the commercialization of SOFCs. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a liquid Sb metal anode solid oxide fuel cell for co-production of olefin and power. The invention proposes to use a liquid Sb metal anode instead of the traditional Ni-YSZ anode. Solid oxide fuel cells using liquid Sb metal anodes have good propane fuel suitability. Due to the density difference, the propane dehydrogenation byproduct, carbon deposition, can be separated from the liquid Sb metal anode. Secondly, the liquid-solid contact surface between the anode and the carbon deposition reduces the carbon deposition problem, increases the oxidation reaction area of the carbon deposition, and is favorable for continuous operation of the battery. In addition, the stirring effect of gas on the liquid anode side is increased by adopting dry propane feeding, carbon deposition separation is accelerated, the power generation product Sb 2O3 is transported, and carbon deposition oxidation reaction is carried out, so that the overall stability of the battery is improved. In order to solve the technical problems, the invention discloses the following technical scheme: use of a solid oxide fuel cell for co-production of olefins and electricity from propane. In some embodiments, the solid oxide fuel cell comprises an electrolyte plate, an anode and a cathode positioned on two sides of the electrolyte plate, wherein the anode comprises liquid Sb metal, the cathode comprises Ba 0.5Sr0.5Co0.8Fe0.2O3-δ, delta is oxygen vacancy content, and the electrolyte plate comprises Ce 0.8Gd0.2O1.9. In some embodiments, the anode and cathode are disposed on both sides of the electrolyte plate and are in communication via a collector line. In some embodiments, the current collector of the anode is a Re wire and the current collector of the cathode is an Ag wire. In the invention, ba 0.5Sr0.5Co0.8Fe0.2O3-δ in the cathode is prepared by a sol-gel method. In some embodiments, the sol-gel process includes mixing and dissolving Ba (NO 3)2、Sr(NO3)2、Co(NO3)2·6H2 O and Fe (NO 3)3·9H2 O), then adding ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water for complexing, and drying and calcining when the mixed solution is gelatinous to obtain a cathode electrode material; in some embodiments, the mass to volume ratio of ethylenediamine tetraacetic acid to aqueous ammonia is 0.30-0.42 g/mL, the mass to volume ratio of citric acid monohydrate to aqueous ammonia is 0.47-0.57 g/mL, in some embodiments, the mixing is dissolved in water, the concentration of aqueous ammonia is 20% -30%, such as 25%, in some embodiments, ba (NO 3)2、Sr(NO3)2、Co(NO3)2·6H2 O and Fe (NO 3)3·9H2 O) are mixed and dissolved, and then heated to 75-85 ℃ before ethylenediamine tetraacetic acid, citric acid monohydrate and aqueous ammonia are added for complexation, in some embodiments, the drying and calcination is performed to obtain a precursor by drying 8-12 h at 170-190 ℃, the obtained precursor is calcined 4-6 h at 900-1100 ℃, in some embodiments, the drying temperature is 180 ℃, the calcining temperature is 1000 ℃, and in some embodiments, the calcining time is h. In the invention, the electrolyte plate is prepared by a dry pressing method. In some embodiments, the dry-pressing method includes dry-pressing the GDC powder to form the electrolyte by physical compression followed by calcination. In some embodiments, the physical pressurization is at a pressure of 1.0 to 1.5 MPa. In some embodiments, the calcination is performed at 1250-1450 ℃ f