CN117039076A - Framework-supported SOFC (solid oxide Fuel cell) suitable for hydrocarbon fuel and preparation method thereof - Google Patents

Framework-supported SOFC (solid oxide Fuel cell) suitable for hydrocarbon fuel and preparation method thereof Download PDF

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CN117039076A
CN117039076A CN202311095483.3A CN202311095483A CN117039076A CN 117039076 A CN117039076 A CN 117039076A CN 202311095483 A CN202311095483 A CN 202311095483A CN 117039076 A CN117039076 A CN 117039076A
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framework
preparing
electrolyte
dripping
powder
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贾礼超
罗俊
刘俨雅
颜冬
李箭
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/109—After-treatment of the membrane other than by polymerisation thermal other than drying, e.g. sintering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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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  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a framework-supported SOFC (solid oxide Fuel cell) suitable for hydrocarbon fuel and a preparation method thereof, and relates to the technical field of solid oxide fuel cells, wherein the preparation method comprises the following steps: preparing a porous framework; preparing a dripping liquid, dripping the dripping liquid on the surface of the framework, and forming a thin electrolyte layer after sintering; preparing a precursor solution, and injecting the precursor solution into a gap in the framework; and (3) screen printing cathode slurry on one side of the electrolyte layer to obtain the framework-supported SOFC. In order to ensure the preparation of an efficient battery, the preparation method comprises several preferred measures: coarsening a framework raw material; selecting and proportioning pore-forming agents; the selection and proportion of the buried baking powder; two sides are coated by dripping; the impregnation mode. The preparation method solves the problem that the traditional Ni-based support battery cannot use hydrocarbon fuel, and different application functions can be realized by selecting different electrolytes and anode impregnating materials.

Description

Framework-supported SOFC (solid oxide Fuel cell) suitable for hydrocarbon fuel and preparation method thereof
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to a framework-supported SOFC (solid oxide Fuel cell) suitable for hydrocarbon fuel and a preparation method thereof.
Background
Solid Oxide Fuel Cells (SOFCs) are a high efficiency, low pollution power generation device. SOFCs may use hydrogen as a fuel or hydrocarbons (e.g., natural gas, liquefied petroleum gas, and high carbon fuel oil) as a fuel. The hydrocarbons have a higher volumetric energy density and lower transportation costs than hydrogen. Therefore, developing the SOFC using hydrocarbon as fuel is beneficial to greatly reducing the volume and cost of the SOFC system, and has great significance for practical application of SOFC.
Currently, a major problem limiting the development of hydrocarbon fuel SOFC technology is that the electrochemical performance of hydrocarbons when used in cells is difficult to stabilize for a long period of time. The most widely studied SOFC anode is a porous cermet composite anode composed of metallic Ni that ensures electrochemical catalytic activity and sufficient electron conductance and an electrolyte material that provides ionic conductance, expanding the three-phase interface. However, ni-based anode supported SOFCs are not suitable for direct use as fuel with hydrocarbons because Ni metal has high activity for c—c bond cleavage, long-term use of hydrocarbon fuel will result in serious carbon deposition on the anode, gradual loss of catalytic activity, and poor test stability.
In recent years, more attention has been directed to oxide fuel electrodes (including fluorite structures, perovskite structures, pyrochlore structures, tungsten bronze structures, and the like) because of their better stability and more excellent anti-carbon deposition properties during hydrocarbon fuel conversion. However, the oxide fuel is extremely incapable of adopting a preparation process of the Ni-based anode. The reason for this is that Ni metal can co-fire with the electrolyte material in the range 1400-1500 ℃ while forming a porous anode and a dense electrolyte. Oxides, particularly the most widely studied perovskite materials with the best electrochemical performance, typically react with the electrolyte at such high cofiring temperatures, and inter-diffusion between the elements results in a change in the original oxide structure or formation of a heterogeneous phase, losing the electrocatalytic function. At present, a battery adopting an oxide fuel electrode is usually in an electrolyte supporting mode, an electrolyte supporting body is firstly prepared at a high temperature, then screen printing or spraying and other modes are adopted on two sides of the electrolyte, and the preparation of the electrode is finished through low-temperature calcination. The relatively low preparation temperature (below 1100 ℃) allows for better chemical compatibility of the electrode with the electrolyte. However, electrolyte supported cells must result in excessive ohmic resistance and the performance of the cell is greatly limited.
Therefore, in order to better use oxides as electrode materials for hydrocarbon fuel SOFCs, changes must be made in the manufacturing process of the electrodes.
Disclosure of Invention
The invention aims to provide a framework-supported SOFC (solid oxide fuel cell) suitable for hydrocarbon fuel and a preparation method thereof, wherein a porous framework which is free of nickel and consists of pure electrolyte materials is prepared, the porous framework is sintered at high temperature to form thin electrolyte, and then an oxide material is injected into gaps of the framework by adopting an impregnation method, so that the problem of high-temperature element diffusion of the oxide and the electrolyte materials is solved. The nickel-free anode support can realize the effective utilization of hydrocarbon fuel, and the thin electrolyte layer has lower ohmic resistance, so that better battery performance compared with the electrolyte support type can be realized.
In order to achieve the above object, the present invention provides a method for preparing a skeletal support type SOFC suitable for hydrocarbon fuel, comprising the steps of:
s1, preparing a porous framework;
s2, preparing a half cell supported by a porous framework;
s3, preparing a precursor solution, dipping the precursor solution into a half cell supported by a porous framework, and then drying and calcining at a low temperature;
s4, repeating the step S3 until reaching a preset impregnation amount;
and S5, printing cathode slurry on one side of an electrolyte layer of the half cell in a screen printing mode, drying and sintering to obtain the framework-supported SOFC.
Preferably, the step S1 includes the steps of:
s1-1, preparing electrolyte original powder by a sol-gel method;
s1-2, calcining and coarsening electrolyte original powder at high temperature;
s1-2, uniformly mixing the calcined and coarsened electrolyte original powder and a pore-forming agent with ethanol solvent according to a certain mass ratio, and drying;
s1-3, weighing a certain amount of dried powder, pressing the powder into slices in a tablet press, and then performing heat treatment to form the porous framework.
Preferably, the step of preparing the half cell supported by the porous skeleton in the step S2 includes:
s2-1, preparing electrolyte;
s2-2, dripping the prepared electrolyte on the surface of the porous framework in a dripping mode, and obtaining the semi-battery supported by the porous framework after high-temperature sintering.
Preferably, the impregnating process in the step S3 is as follows: firstly, one surface of a framework in a half cell supported by a porous framework faces upwards, and then, a precursor solution is dripped on the surface of the framework to enable the surface of the framework to be completely covered by the precursor solution.
Preferably, the mass ratio of the pore-forming agent to the electrolyte raw powder in the step S1 is 3:5, the pore-forming agent is carbon powder and corn starch, and the mass ratio of the carbon powder to the corn starch is 1:1.
preferably, the dripping mode in the step S2 is double-sided dripping, the number of times of dripping is controlled according to the thickness of the electrolyte, and a small amount of dripping is uniformly dripped on the porous framework by a dropper for a plurality of times.
Preferably, the high temperature sintering in the step S2-2 comprises burial sintering, wherein the burial sintering powder used in the burial sintering is mixed powder containing 10wt.% of NiO and 90wt.% of electrolyte original powder.
Preferably, the preset impregnation amount in the step S4 is 20% -50% of the mass of the half cell supported by the porous skeleton.
The invention provides a framework-supported SOFC prepared according to the preparation method.
Therefore, the framework-supported SOFC suitable for hydrocarbon fuel and the preparation method thereof have the following beneficial effects:
(1) Ni metal pairThe carbon-hydrogen fuel has strong breaking capacity, and is extremely easy to cause the carbon deposition of the anode to be deactivated. The framework-type supporting SOFC without nickel provided by the invention can ensure the effective utilization of hydrocarbon fuel and has better long-term stability. When the anode framework and the electrolyte adopt oxygen ion conductor materials, hydrocarbon fuel can completely react with oxygen ions through the catalysis of oxide materials impregnated on the framework to generate CO 2 And H 2 O, avoid the active metal (such as Ni) to be too high in activity to cause carbon deposition; when the anode skeleton and the electrolyte are made of proton conductor materials, additional functions such as co-production of ethylene and electric energy can be achieved (process of introducing C at the anode 2 H 6 ，C 2 H 6 Changing into H under the catalysis of anodic oxide material 2 And C 2 H 4 (if the anode is Ni, ni with high C-C bond cleavage activity will C 2 H 6 Direct conversion to C and H 2 )，H 2 Is effectively utilized at the anode to generate electric energy, C 2 H 4 Cannot be catalyzed by oxide anode materials and is collected in tail gas. Thereby the framework-supported SOFC without nickel can realize the C with low chemical value 2 H 6 Is converted into C with high chemical value 2 H 4 Electrical energy); CO-production of CO and electrical energy (CH being fed at anode 4 And CO 2 Two greenhouse gases are changed into H under the catalysis of anode materials 2 And CO, H 2 The anode is effectively utilized to generate electric energy, the unutilized CO is collected from the tail gas, and the problems of the future greenhouse effect are effectively solved, and meanwhile, the high-concentration CO is produced and the electric energy is obtained).
(2) The pore-forming agent is selected and proportioned to facilitate the formation of interconnected non-flat pores. If the pore-forming agent is only corn starch, flat pores are easily formed in the framework, so that the impregnation and gas transmission are not facilitated; if only carbon powder is used, closed pores which are not communicated are formed in the framework, and gas cannot be impregnated and transported. The mass ratio of the pore-forming agent to the electrolyte raw powder explored in the invention is 3/5, and if the ratio of the pore-forming agent is increased again, the porosity in the framework is too high, and the support body does not have enough strength.
(3) The invention has wide selection range of materials, and can select corresponding framework materials and impregnated anode materials according to different requirements. The impregnation method has two advantages: 1. the precursor solution is uniformly distributed on the framework through impregnation, and compared with mechanical mixing, more three-phase interfaces can be provided for the anode; 2. the impregnation method requires a low degree of thermal expansion matching between the matrix material and the impregnated material.
(4) The burial firing method provided by the invention is beneficial to solving the problem of sintering densification of the electrolyte.
(5) The double-sided drip coating method provided by the invention is beneficial to solving the problem of bending of the battery.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a skeleton morphology of a non-coarsened and coarsened BZCY raw powder, wherein a is a skeleton morphology of a non-coarsened BZCY raw powder, and b is a skeleton morphology of a coarsened BZCY raw powder;
FIG. 2 is a morphology diagram of a porous framework obtained by taking corn starch as a pore-forming agent;
FIG. 3 is a morphology diagram of a porous framework obtained by taking carbon powder as a pore-forming agent;
FIG. 4 is a graph showing the final sintering results of single-sided and double-sided dispensing according to the present invention, wherein the left side is double-sided dispensing and the right side is single-sided dispensing;
FIG. 5 is a topography of the skeleton before and after impregnation of the anode material; wherein a is a topography diagram before the framework is impregnated with anode materials; b is a topography diagram before the framework is impregnated with anode materials;
FIG. 6 is a graph of the impedance of a cell impregnated with 20% anode material at different temperatures in a hydrogen atmosphere;
FIG. 7 is a graph of the discharge power density of a cell impregnated with 20% anode material at different temperatures in a hydrogen atmosphere;
FIG. 8 is a graph of the impedance of a cell impregnated with 20% anode material using an atmosphere of hydrogen and ethane at an operating temperature of 750 ℃;
FIG. 9 is a graph of the discharge power density of a cell impregnated with 20% anode material using a hydrogen and ethane atmosphere at an operating temperature of 750 ℃;
FIG. 10 shows that a cell impregnated with 20% anode material is not subjected to current and is subjected to 500mA cm, respectively, at an operating temperature of 750deg.C 2 Ethane conversion, ethylene selectivity and ethylene yield after current of (a) are plotted.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The invention provides a preparation method of a framework-supported SOFC (solid oxide Fuel cell) suitable for hydrocarbon fuel, which comprises the following steps:
s1, preparing electrolyte original powder by a sol-gel method; calcining and coarsening the electrolyte original powder at high temperature; the calcined and coarsened electrolyte original powder, carbon powder and the corn starch are mixed according to the mass ratio of 5:1.5:1.5, uniformly mixing the mixture with ethanol solvent and drying; weighing a certain amount of dried powder, pressing the powder into slices in a tablet press, and then performing heat treatment to form a porous framework;
s2, mixing the electrolyte original powder in the step S1 with ethanol, polyethylene glycol, triethanolamine, dibutyl phthalate, polyvinyl butyral and the like according to a mass ratio of 1:0.05:0.05:0.05:0.05:8, uniformly mixing and ball milling for 18-24 hours to obtain electrolyte; dripping the prepared electrolyte onto the porous framework in a dripping mode, and sintering at high temperature to obtain a semi-battery supported by the porous framework; the mode of dripping is two-sided dripping, the number of times is controlled according to the electrolyte thickness, a small amount of droppers are used for uniformly dripping on a porous framework, after the porous framework is dripped on one side and naturally dried, electrolyte with the same number of times is dripped on the other side, because the porous framework and the electrolyte are made of the same material, but the porosity of the porous framework and the electrolyte are different, the shrinkage rate in the high-temperature sintering process is different, the framework is concave and the electrolyte is convex after sintering, and the curved battery is unfavorable for testing. The purpose of the two-side dripping is to ensure the balance of thermal stress on the two sides of the porous framework and ensure the flatness of the sintered battery. And correspondingly, polishing the electrolyte on one side by using sand paper after sintering to obtain the half cell supported by the porous framework.
The high-temperature sintering comprises burial sintering, wherein burial sintering powder used by burial sintering is mixed powder containing 10wt.% of NiO and 90wt.% of electrolyte original powder, and aims to ensure electrolyte sintering compactness by utilizing diffusion effect of NiO at high temperature and sintering assisting effect of NiO on an electrolyte sintering process.
S3, preparing a precursor solution, namely sucking a certain amount of the precursor solution from one surface of a framework in a half cell supported by a porous framework by using a dropper, dripping the precursor solution on the surface of the framework and ensuring that the precursor solution is completely covered by the framework, then placing the framework in a vacuum machine, vacuumizing to ensure that gaps in the framework are completely full of the precursor solution, wiping off superfluous liquid on the surface, and placing the framework in a muffle furnace for low-temperature calcination, wherein the calcination temperature is 400-500 ℃.
S4, repeating the step S3 until the mass of the half battery supported by the porous framework with the preset impregnation amount reaches 20% -50%;
and S5, printing cathode slurry on one side of an electrolyte layer of the half cell in a screen printing mode, drying and sintering to obtain the framework-supported SOFC.
The invention provides a skeleton-supported SOFC (solid oxide Fuel cell) prepared by a preparation method of the skeleton-supported SOFC taking hydrocarbon as fuel.
Examples
The invention focuses on the innovation of the preparation technology. The materials of the electrolyte and the porous framework in the embodiment are BZCY (BaZr) 0.1 Ce 0.7 Y 0.2 O 3 ) Materials, if modified to other electrolyte materials (e.g., YSZ, GDC, etc.) only in material selection, should be considered equivalent substitutions of the present invention; the oxide impregnated on the porous skeleton is selected from PrBa 0.95 (Fe 0.8 Ni 0.2 ) 1.8 Mo 0.2 O 5+δ Perovskite materials, if modified to other oxide materials only in material selection, should be considered equivalent substitutions of the present invention; the cathode material is LSCF (La) 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 ) Materials, if only material selection is changed to other cathode materials, should be considered equivalent alternatives to the present invention. The framework-supported SOFC provided in this embodiment can realize the following functions: ethane is introduced at the anode, ethane at (PrBa) 0.95 (Fe 0.8 Ni 0.2 ) 1.8 Mo 0.2 O 5+δ Dehydrogenation to produce C under catalysis of perovskite material 2 H 6 And H 2 ，H 2 Is utilized by SOFC to generate electric energy, and C is not utilized 2 H 4 And collecting the tail gas to realize the co-production of electric energy and ethylene. If the electrolyte is changed into oxygen ion conduction type, the preparation process can realize the effective utilization of hydrocarbon fuel.
S1, nitrate such as barium nitrate, zirconium nitrate pentahydrate, cerium nitrate hexahydrate and yttrium nitrate hexahydrate is mixed according to a molar ratio of 1:0.1:0.7: dissolving 0.2 in deionized water, adding 1-time of ethylenediamine tetraacetic acid in the molar quantity of metal ions, dropwise adding ammonia water into the solution to dissolve the ethylenediamine tetraacetic acid, adding 2-time of citric acid monohydrate in the molar quantity of metal ions, dropwise adding ammonia water to adjust the pH value to 7-8, and stirring in an oil bath pot at 80 ℃ until gel is formed. Then placing the gel in an oven, setting the temperature to 280 ℃, preserving the temperature for 6 hours to obtain precursor powder, grinding and calcining at 1000 ℃ for 3 hours to obtain the electrolyte BZCY original powder.
S2, pretreating the electrolyte BZCY original powder for 3 hours at a calcination temperature of 1300 ℃ to coarsen crystal grains so as to reduce sintering activity of the electrolyte BZCY original powder in the electrolyte sintering process. If the skeleton is directly prepared from the electrolyte raw powder, serious agglomeration occurs in the electrolyte sintering process, and the comparison between the two is shown in figure 1, wherein a is the skeleton prepared from the BZCY raw powder which is not coarsened, obvious compact blocks are arranged in the skeleton, the gas transmission is very unfavorable, and b is the skeleton prepared from the BZCY raw powder which is coarsened, and the pores in the skeleton are loose and uniformly distributed, so that the gas transmission is favorable. Coarsened electrolyte BZCY original powder, carbon powder and corn starch are mixed according to the mass ratio of 5:1.5: mixing the mixture with ethanol solvent in a proportion of 1.5, and ball milling for 6-8 hours at a ball milling speed of 250r/min. After ball milling, the mixture is placed in an oven, and the temperature is set at 80 ℃ and kept until the mixture is dried. Weighing 0.5g of dried powder, pouring into a die of a tablet press, pressurizing to 10Mpa, maintaining the pressure for 1 minute to obtain a sheet with the diameter of 15mm, and calcining the sheet at 1000 ℃ for 3 hours to obtain the BZCY porous skeleton. If the pore-forming agent is only corn starch, flat pores are easily formed in the framework, which is unfavorable for impregnation and gas transmission (as shown in figure 2); if only carbon powder is used, closed cells which are not communicated are formed in the framework, and gas cannot be impregnated and transported (as shown in fig. 3).
S3, mixing the electrolyte BZCY original powder with polyethylene glycol, triethanolamine, dibutyl phthalate, polyvinyl butyral, solvent ethanol and the like according to a mass ratio of 1:0.05:0.05:0.05:0.05:8, ball milling for 18 hours after uniformly mixing the materials in proportion, wherein the ball milling speed is 250r/min, and the BZCY electrolyte is obtained. A small amount of electrolyte is sucked by a dropper and is dripped on the surface of the BZCY porous skeleton, and the electrolyte uniformly flows on the BZCY porous skeleton by slow left-right shaking until the electrolyte is completely dried, and then the BZCY porous skeleton is dried in an oven at 80 ℃. And (3) dripping electrolyte solution on the other side of the porous framework for the same times in the same manner so as to ensure that the contraction stress of the two sides is the same in the sintering process. And (3) burying the BZCY porous framework after dripping in mixed powder containing 10wt.% of NiO and 90wt.% of electrolyte original powder, placing the mixed powder in a high-temperature furnace, calcining the mixed powder at 1400 ℃ for 10 hours, and polishing an electrolyte layer on one side of the porous framework by 400-mesh sand paper after sintering to obtain the half battery supported by the porous framework. The final sintering results of single-side drop coating and double-side drop coating are shown in fig. 4, the left side is measured as a half cell after double-side drop coating, the two sides of the half cell are flat, the assembly of a screen printing step of a subsequent cathode material and a cell test fixture is facilitated, the right side is the half cell after single-side drop coating, the whole cell is bent from the outer side to the center, and the assembly of the screen printing and the fixture is not facilitated.
S4, nitrate such as praseodymium nitrate hexahydrate, barium nitrate, ferric nitrate nonahydrate, nickel nitrate hexahydrate and ammonium heptamolybdate is mixed according to the molar ratio of 0.95:0.95:1.44:0.36:0.2 is dissolved in deionized water, then ethylenediamine tetraacetic acid with the molar weight of 1 time of the metal ions is added, and then ammonia water is added dropwise into the solution, and the PH is regulated to 7-8, so as to obtain a precursor solution. The initial weight of the half cell supported by the porous framework is weighed, one surface of the framework in the half cell supported by the porous framework faces upwards, a certain amount of precursor solution is sucked by a dropper and is dripped on the surface of the framework, the framework is ensured to be completely covered by the precursor solution, then the framework is placed in a vacuum machine to be vacuumized, so that gaps inside the framework are completely filled with the precursor solution, and the framework is placed in a muffle furnace to be calcined for 30 minutes at 400 ℃ after superfluous liquid on the surface is wiped off. The dipping operation is repeated until the dipping amount reaches 20% -50%. The impregnated amount of the embodiment is 20%, the morphology of the impregnated skeleton is shown in fig. 5, the surface of the impregnated skeleton is covered with a film formed by an impregnating material, and the impregnated skeleton is in good contact with the skeleton, so that the length of a three-phase interface is prolonged, and the number of reactive sites is increased.
S5, nitrate such as lanthanum nitrate hexahydrate, strontium nitrate, cobalt nitrate hexahydrate and ferric nitrate nonahydrate is mixed according to the molar ratio of 0.6:0.4:0.2: dissolving 0.8 in deionized water, adding 1-time of ethylenediamine tetraacetic acid in the molar quantity of metal ions, dropwise adding ammonia water into the solution to dissolve the ethylenediamine tetraacetic acid, adding 2-time of citric acid monohydrate in the molar quantity of metal ions, dropwise adding ammonia water to adjust the pH value to 7-8, and stirring in an oil bath pot at 80 ℃ until gel is formed. Then placing the gel in an oven, setting the temperature to 280 ℃, preserving the temperature for 6 hours, grinding the obtained precursor powder, and calcining at 1000 ℃ for 3 hours to obtain LSCF powder. Ethylcellulose was dissolved in terpineol to make an ethylcellulose terpineol solution with an ethylcellulose content of 4wt.% as a binder for formulating screen printing pastes. Mixing LSCF powder, BZCY original powder and a binder according to a mass ratio of 6:4:10, preparing cathode slurry, grinding for 2 hours until the cathode slurry is uniform, screen printing on one side of electrolyte in a half cell supported by a porous framework, drying, and repeating printing for 2 times. The half cell obtained was placed in a muffle furnace and calcined at 1000 ℃ for 2 hours to obtain a skeletal support SOFC.
Electrochemical tests were performed on the skeletal support SOFC prepared in this example. In the hydrogen atmosphere, the impedance spectra of the single cell at different temperatures are shown in FIG. 6, the ohmic impedance and the polarization impedance of the single cell are increased along with the decrease of the temperature, and the ohmic impedance and the polarization impedance of the single cell are respectively 0.548/0.284 Ω & cm at the working temperature of 750 DEG C 2 The method comprises the steps of carrying out a first treatment on the surface of the Single cellThe discharge power densities at different temperatures are shown in FIG. 7, and the maximum power densities at 750deg.C/700deg.C/650deg.C are 296/219/150mW cm, respectively 2 . The impedance spectrum of the single cell at 750℃under hydrogen and ethane atmosphere is shown in FIG. 8, and the ohmic and polarization impedances of the single cell under ethane atmosphere are 0.628/0.406. Omega. Cm, respectively 2 Resistance to the atmosphere of hydrogen becomes larger because ethane is more difficult to activate by the electrode; the discharge power density of the unit cell under hydrogen and ethane atmospheres is shown in FIG. 9, and the maximum power densities are 296/248 mW.cm, respectively 2 The reason why the power density in an ethane atmosphere is relatively low is that: 1. the impedance of the single cell is larger under the ethane atmosphere; 2. the hydrogen partial pressure in the ethane atmosphere is lower than that of pure hydrogen, resulting in a decrease in the open circuit voltage of the unit cell in the ethane atmosphere. The single cell is not loaded with current and is loaded with 500mA cm at the working temperature of 750 DEG C 2 The conversion of ethane, the selectivity of ethylene and the yield of ethylene were 37.9%/42.2%, 90.6%/92.1%, 34.3%/38.9%, respectively, as shown in fig. 10, the improvement of the conversion of ethane was due to the fact that protons generated by the dehydrogenation reaction of ethane catalyzed by the anode were transferred to the cathode through the electrolyte, and the continuous decrease of the reaction products led to the forward progress of the dehydrogenation reaction of ethane, thereby improving the conversion of ethane; the improvement in ethylene selectivity is due to the fact that ethane also undergoes hydrogenation side reactions at high temperatures to produce methane, and the conversion rate of the reaction decreases with decreasing hydrogen concentration at the anode side, and the methane produced decreases, thereby improving the ethylene selectivity.
Therefore, the framework-supported SOFC suitable for hydrocarbon fuel and the preparation method thereof have good power output under the hydrogen and ethane atmosphere. When ethane is used as fuel, the anode immersed in the framework catalyzes ethane into ethylene, hydrogen ions and electrons, the hydrogen ions are transmitted to the cathode through the electrolyte and react with oxygen at the cathode and electrons transmitted by an external circuit to generate water, so that an electric loop is formed, and the function of outputting electric energy is realized; and the residual ethylene in the tail gas is collected, so that the co-production of electric energy and ethylene is realized. The invention adopts an anode supporting mode to help reduce the thickness of electrolyte and reduce the ohmic impedance of single cells; the adoption of the mode of adding the impregnated electrode into the framework instead of the classical anode support contains 60% of nickel is beneficial to preventing the excessive catalysis of nickel and realizing the effective utilization of hydrocarbon fuel.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.

Claims (9)

1. A method for preparing a skeletal support SOFC suitable for hydrocarbon fuels, comprising the steps of:
s1, preparing a porous framework;
s2, preparing a half cell supported by a porous framework;
s3, preparing a precursor solution, dipping the precursor solution into a half cell supported by a porous framework, and then drying and calcining at a low temperature;
s4, repeating the step S3 until reaching a preset impregnation amount;
and S5, printing cathode slurry on one side of an electrolyte layer of the half cell in a screen printing mode, drying and sintering to obtain the framework-supported SOFC.
2. The method for preparing a skeletal support SOFC for hydrocarbon fuels according to claim 1, wherein the step S1 comprises the steps of:
s1-1, preparing electrolyte original powder by a sol-gel method;
s1-2, calcining and coarsening electrolyte original powder at high temperature;
s1-2, uniformly mixing the calcined and coarsened electrolyte original powder and a pore-forming agent with ethanol solvent according to a certain mass ratio, and drying;
s1-3, weighing a certain amount of dried powder, pressing the powder into slices in a tablet press, and then performing heat treatment to form the porous framework.
3. The method for preparing a skeletal support SOFC for hydrocarbon fuels according to claim 1, wherein the step of preparing a porous skeletal support half cell in step S2 comprises the steps of:
s2-1, preparing electrolyte;
s2-2, dripping the prepared electrolyte on the surface of the porous framework in a dripping mode, and obtaining the semi-battery supported by the porous framework after high-temperature sintering.
4. The method for preparing a skeletal support SOFC for hydrocarbon fuels according to claim 1, wherein the impregnation in step S3 is: firstly, one surface of a framework in a half cell supported by a porous framework faces upwards, and then, a precursor solution is dripped on the surface of the framework to enable the surface of the framework to be completely covered by the precursor solution.
5. The method for producing a skeletal support SOFC for hydrocarbon fuels according to claim 2, characterized by: the mass ratio of the pore-forming agent to the electrolyte raw powder in the step S1 is 3:5, the pore-forming agent is carbon powder and corn starch, and the mass ratio of the carbon powder to the corn starch is 1:1.
6. a method of preparing a skeletal support SOFC for hydrocarbon fuels according to claim 3, characterized by: the dripping mode in the step S2 is double-sided dripping, the number of times of dripping is controlled according to the thickness of the electrolyte, and a small amount of dripping pipes are used for uniformly dripping on the porous framework for many times.
7. A method of preparing a skeletal support SOFC for hydrocarbon fuels according to claim 3, characterized by: the high-temperature sintering in the step S2-2 comprises burial sintering, wherein burial sintering powder used in burial sintering is mixed powder containing 10wt.% of NiO and 90wt.% of electrolyte original powder.
8. The method for preparing a skeletal support SOFC for hydrocarbon fuels according to claim 1, characterized by: the preset impregnation amount in the step S4 is 20-50% of the mass of the half cell supported by the porous framework.
9. A skeletal support SOFC prepared by the method of preparing a skeletal support SOFC for hydrocarbon fuels of any one of claims 1-8.
CN202311095483.3A 2023-08-29 2023-08-29 Framework-supported SOFC (solid oxide Fuel cell) suitable for hydrocarbon fuel and preparation method thereof Pending CN117039076A (en)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2007115536A (en) * 2005-10-20 2007-05-10 Tokyo Electric Power Co Inc:The Manufacturing method of electrode for porous solid oxide fuel cell
CN101083324A (en) * 2007-06-22 2007-12-05 中国科学技术大学 Solid-oxide fuel battery complex cathode and method for making same
CN101136478A (en) * 2007-08-31 2008-03-05 哈尔滨工业大学 Process for producing anode support
CN114023979A (en) * 2021-10-29 2022-02-08 华中科技大学 Metal support solid oxide fuel cell and preparation method thereof
CN115084549A (en) * 2022-08-18 2022-09-20 佛山仙湖实验室 Nano perovskite electrode for solid oxide battery and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007115536A (en) * 2005-10-20 2007-05-10 Tokyo Electric Power Co Inc:The Manufacturing method of electrode for porous solid oxide fuel cell
CN101083324A (en) * 2007-06-22 2007-12-05 中国科学技术大学 Solid-oxide fuel battery complex cathode and method for making same
CN101136478A (en) * 2007-08-31 2008-03-05 哈尔滨工业大学 Process for producing anode support
CN114023979A (en) * 2021-10-29 2022-02-08 华中科技大学 Metal support solid oxide fuel cell and preparation method thereof
CN115084549A (en) * 2022-08-18 2022-09-20 佛山仙湖实验室 Nano perovskite electrode for solid oxide battery and preparation method thereof

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