CN111554956B - LST-SDC-NCAL composite material and application thereof, single-layer fuel cell and preparation method thereof - Google Patents
LST-SDC-NCAL composite material and application thereof, single-layer fuel cell and preparation method thereof Download PDFInfo
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- 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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
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- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
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- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
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Abstract
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to an LST-SDC-NCAL composite material, a single-layer fuel cell, and a preparation method and application thereof. The invention provides an LST-SDC-NCAL composite material which comprises a uniformly mixed chemical composition of La0.25Sr0.75Ti1O3‑δThe LST component and the chemical composition of the cerium-based rare earth element are Ce0.8Sm0.2O2‑xThe SDC component and the chemical composition of the catalyst are Ni0.8Co0.15Al0.05LiO2‑yThe NCAL component of (a); the mass ratio of the LST component to the SDC component to the NCAL component is (1-5): (3-5): (1-5); δ, x and y are values that keep the compound electrically neutral. The LST-SDC-NCAL composite material provided by the invention has no layering phenomenon between the electrode and the electrolyte and has good power output.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to an LST-SDC-NCAL composite material, application thereof, a single-layer fuel cell and a preparation method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is a power generation device that directly converts chemical energy stored in a fuel and an oxidant into electrical energy, and has the advantages of high energy conversion efficiency, cleanliness, no pollution, strong fuel adaptability, and the like. The membrane electrode assembly of the traditional solid oxide fuel cell consists of three layers of an anode, an electrolyte and a cathode. The electrode is very easily peeled off from the electrolyte layer due to the difference in thermal expansion coefficient between the electrode and the electrolyte layer. In order to reduce the difference in thermal expansion coefficient between the electrolyte and the electrode, researchers have generally adopted a composite of a catalyst and an ionic conductor as the electrode [ Changnong Xia and Meilin Liu0.1Ce0.9O1.95 fabricated by dry pressing,Solid State Ionics,2001,144:249-255]. However, since the electrode material is not completely the same as the electrolyte material, delamination is still unavoidable. Zhu et al [ Bin Zhu, Ying Ma, Xiaodi Wang, et al, A fuel cell with a single component functioning as the electrodes and electrodes, electronics Communications,2011,13,225-]The anode, electrolyte and cathode of the single-layer fuel cell have the same material, so that the membrane electrode layering phenomenon can be effectively avoided.
Therefore, a membrane electrode material of a solid oxide fuel cell, which can solve the delamination phenomenon caused by the mismatch of the thermal expansion coefficients between the electrode and the electrolyte and has good power output, is sought, and has important economic significance and industrial value.
Disclosure of Invention
In view of the above, the present invention provides an LST-SDC-NCAL composite material, which has no delamination between electrodes and electrolyte and has good power output; the invention also provides a preparation method and application of the LST-SDC-NCAL composite material.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides an LST-SDC-NCAL composite material, which comprises an LST component, an SDC component and an NCAL component which are uniformly mixed; the mass ratio of the LST component to the SDC component to the NCAL component is (1-5): (3-5): (1-5);
the LST component has a chemical composition of La0.25Sr0.75Ti1O3-δChemical composition Ce of the SDC component0.8Sm0.2O2-xThe chemical composition of the NCAL component is Ni0.8Co0.15Al0.05LiO2-yAnd δ, y and z are values that keep the compound electrically neutral.
Preferably, the LST component is prepared by a process comprising the steps of:
mixing lanthanum oxide, strontium carbonate and nitric acid to obtain a first mixture;
mixing a glycol solution of titanium isopropoxide with citric acid to obtain a second mixture;
and mixing the first mixture and the second mixture, sequentially carrying out first heating, heat preservation and temperature rise, then carrying out second heating, heat preservation, grinding and sintering to obtain the LST component.
Preferably, the volume ratio of titanium isopropoxide to ethylene glycol in the ethylene glycol solution of titanium isopropoxide is 1: (2-8); the molar ratio of the ethylene glycol solution of titanium isopropoxide to citric acid is 1: (1-6).
Preferably, the mixing time of the first mixture and the second mixture is 8-20 h;
the temperature of the first heating and heat preservation is 50-90 ℃, and the time is based on the obtained gel;
the temperature of the second heating and heat preservation is 400-600 ℃, and the time is 1.5-4 hours;
the sintering temperature is 1100-1300 ℃, and the sintering time is 4-7 h.
Preferably, the SDC component is prepared by a process comprising the steps of:
mixing cerium nitrate, samarium nitrate and water to obtain a cerium-samarium mixed solution;
adding a sodium carbonate solution into the cerium-samarium mixed solution, stirring and standing to obtain a solid-liquid mixture;
and carrying out solid-liquid separation on the solid-liquid mixture, and sequentially washing, drying and calcining the obtained solid to obtain the SDC component.
Preferably, the concentration of total metal ions in the cerium-samarium mixed solution is 0.5-2 mol/L; the concentration of the sodium carbonate solution is 0.5-2 mol/L;
the molar ratio of total metal ions in the cerium-samarium mixed solution to carbonate in the sodium carbonate solution is 1: (1.2-2.5).
Preferably, the stirring time is 1-5 h; the standing time is 6-20 h; the pH value of the washed product is 7-8;
the drying temperature is 100-150 ℃, and the drying time is 6-20 h;
the calcining temperature is 750-900 ℃, and the time is 3-6 h.
The invention also provides application of the LST-SDC-NCAL composite material in the technical scheme in a solid oxide fuel cell, which is characterized in that the LST-SDC-NCAL composite material is used as an anode, a solid electrolyte and a cathode of the solid oxide fuel cell.
The invention also provides a single-layer fuel cell, which comprises an anode, a solid electrolyte and a cathode, wherein the cathode and the anode are independently foamed nickel loaded with the LST-SDC-NCAL composite material, and the solid electrolyte is the LST-SDC-NCAL composite material; the LST-SDC-NCAL composite material is the LST-SDC-NCAL composite material in the technical scheme.
The invention also provides a preparation method of the single-layer fuel cell, which comprises the following steps:
mixing the LST-SDC-NCAL composite material with terpineol to obtain slurry;
coating one side of the slurry on the surface of the foamed nickel, and drying to obtain the foamed nickel loaded with the LST-SDC-NCAL composite material;
and sequentially laminating and pressing the foamed nickel loaded with the LST-SDC-NCAL composite material, the LST-SDC-NCAL composite material and the foamed nickel loaded with the LST-SDC-NCAL composite material to obtain the single-layer fuel cell.
The invention provides an LST-SDC-NCAL composite material, which comprises an LST component, an SDC component and an NCAL component which are uniformly mixed; the mass ratio of the LST component to the SDC component to the NCAL component is (1-5): (3-5): (1-5); the LST component has a chemical composition of La0.25Sr0.75Ti1O3+δThe chemical composition of the SDC component is Ce0.8Sm0.2O2-xThe chemical composition of the NCAL component is Ni0.8Co0.15Al0.05LiO2-yAnd δ, y and z are values that keep the compound electrically neutral. The LST-SDC-NCAL composite material provided by the invention is a semiconductor ion composite material, wherein LST is a hydrogen oxidation catalyst, SDC is an oxygen ion conductor, and NCAL is an oxygen reduction catalyst. The single-layer fuel cell obtained based on the LST-SDC-NCAL composite material provided by the invention can simultaneously provide the electrode and the electrolyte of the membrane electrode in the solid oxide fuel cell, namely the LST-SDC-NCAL composite material simultaneously provides the electrode and the electrolyte, so that the layering phenomenon of the solid oxide fuel cell caused by the mismatching of the thermal expansion coefficients of different layers can be effectively avoided, the stability of the solid oxide fuel cell is favorably improved, and the power output is improved.
The test results of the examples show that the open circuit voltage of the single-layer fuel cell obtained by using the LST-SDC-NCAL composite material provided by the invention as the membrane electrode component is higher than 1V and the power density is 222mW cm under the test temperature condition of 550 DEG C-2The single-layer fuel cell provided by the invention has the advantages of no short circuit, considerable output performance, no layering and high stability.
Drawings
FIG. 1 shows La of example 10.25Sr0.75Ti1O3+δSEM picture of (1);
FIG. 2 is Ce in example 10.8Sm0.2O2-xSEM picture of (1);
FIG. 3 shows Ni in example 10.8Co0.15Al0.05LiO2-ySEM picture of (1);
FIG. 4 is an XRD pattern of LST, SDC, NCAL and mixed powders thereof in example 1;
FIG. 5 is an I-V curve and an I-P curve of a single-layer fuel cell obtained in application example 1 at different temperatures;
FIG. 6 is an EIS spectrum of the single-layer fuel cell obtained in application example 1 at different temperatures, wherein the diagram is 0-2.5 Ω & cm2(ii) a close-up view within the scope;
fig. 7 is a stability test chart of the single layer fuel cell obtained in application example 1.
Detailed Description
The invention provides an LST-SDC-NCAL composite material, which comprises an LST component, an SDC component and an NCAL component which are uniformly mixed; the mass ratio of the LST component to the SDC component to the NCAL component is (1-5): (3-5): (1-5), preferably (2-4): (3.5-4.5): (2-4), most preferably 3:4: 3; the LST component has a chemical composition of La0.25Sr0.75Ti1O3-δThe chemical composition of the SDC component is Ce0.8Sm0.2O2-xThe chemical composition of the NCAL component is Ni0.8Co0.15Al0.05LiO2-yAnd δ, x and y are values at which the compound remains electrically neutral.
In the present invention, the LST component is preferably prepared by a process comprising the steps of:
mixing lanthanum oxide, strontium carbonate and dilute nitric acid to obtain a first mixture;
mixing a glycol solution of titanium isopropoxide with citric acid to obtain a second mixture;
and mixing the first mixture and the second mixture, and then sequentially carrying out first heating and heat preservation, heating and then carrying out second heating and heat preservation, grinding and sintering to obtain the LST component.
Lanthanum oxide, strontium carbonate and nitric acid are mixed to obtain a first mixture. In the present invention, the molar ratio of lanthanum oxide to strontium carbonate is preferably 1: 6. in the present invention, the lanthanum oxide is preferably a lanthanum oxide powder; the strontium carbonate is preferably strontium carbonate powder; the particle size of the lanthanum oxide powder and the strontium carbonate powder is not particularly limited in the present invention, and those known to those skilled in the art may be used. In the invention, the concentration of the dilute nitric acid is preferably 0.5-1.5 mol/L, more preferably 0.7-1.3 mol/L, and still more preferably 0.8-1.2 mol/L. The dosage of the dilute nitric acid is not specially limited, so that the lanthanum oxide and the strontium carbonate can be fully dissolved. The mixing is not particularly limited in the present invention, and may be performed by mixing well known to those skilled in the art, specifically, stirring; the stirring is not particularly limited in the present invention, and a stirring known to those skilled in the art may be employed.
The invention mixes a glycol solution of titanium isopropoxide with citric acid to obtain a second mixture. In the present invention, the volume ratio of titanium isopropoxide to ethylene glycol in the ethylene glycol solution of titanium isopropoxide is preferably 1: (2-8), more preferably 1: (3-7), and more preferably 1: (4-6). In the present invention, the molar ratio of the ethylene glycol solution of titanium isopropoxide to citric acid is preferably 1: (1 to 6), more preferably 1: (2-5), and more preferably 1: (3-4). In the present invention, the mixing of the ethylene glycol solution of titanium isopropoxide and citric acid is preferably performed by adding citric acid to the ethylene glycol solution of titanium isopropoxide.
After a first mixture and a second mixture are obtained, the LST component is obtained by mixing the first mixture and the second mixture, sequentially carrying out first heating and heat preservation, heating, then carrying out second heating and heat preservation, grinding and sintering. In the present invention, the mixing is preferably performed under stirring; the mixing time is preferably 8-20 h, more preferably 10-18 h, and further preferably 12-16 h. The invention is beneficial to the full contact and aggregation of all the component elements through mixing, thereby being beneficial to the synthesis of the LST component.
In the invention, the temperature of the first heating and heat preservation is preferably 50-90 ℃, more preferably 55-85 ℃, and further preferably 60-80 ℃; in the present invention, the time for the first heat-holding is not particularly limited, and the gel obtained is used as a standard. In the present invention, the gel is brown. In the present invention, the first heat-holding is preferably performed under stirring; the stirring is not particularly limited in the present invention, and a stirring known to those skilled in the art may be employed. In the present invention, the first heating and heat-preserving device is preferably an oven. According to the invention, the evaporation of the solvent in the mixed system is promoted through the first heating and heat preservation, and the brown gel is formed.
In the invention, the temperature of the second heating and heat preservation is preferably 400-600 ℃, more preferably 420-580 ℃, and further preferably 450-550 ℃; the time is preferably 1.5 to 4 hours, more preferably 2 to 3.5 hours, and still more preferably 2.5 to 3 hours. In the present invention, the second heat-retaining device is preferably a muffle furnace. The second heating and heat preservation temperature is preferably obtained by heating; in the invention, the heating rate is preferably 2-8 ℃/min, more preferably 2-7 ℃/min, and still more preferably 3-6 ℃/min. The invention further dries the gel through the second heating and heat preservation to obtain the solid substance.
The present invention is not particularly limited to the above-mentioned grinding, and a grinding known to those skilled in the art may be used. The invention refines the obtained solid substance into powder from block by grinding. The particle size of the product obtained by grinding is not particularly limited in the present invention, and the particle size of the product obtained by grinding can be adjusted to a powder state as is well known to those skilled in the art.
In the invention, the sintering temperature is preferably 1100-1300 ℃, more preferably 1120-1280 ℃, and further preferably 1150-1250 ℃; the time is preferably 4 to 7 hours, more preferably 4.5 to 6.5 hours, and still more preferably 5 to 6 hours. The invention is beneficial to the decomposition reaction and removal of impurities in the LST component through sintering so as to obtain the pure-phase LST component; while facilitating improved uniformity and densification of the LST component. In the present invention, the LST component is a white powder. In the invention, the LST component preferably has a particle size of 20 to 300 nm.
In the present invention, the SDC component is preferably prepared by a process comprising the steps of:
mixing cerium nitrate, samarium nitrate and water to obtain a cerium-samarium mixed solution;
adding a sodium carbonate solution into the cerium-samarium mixed solution, stirring and standing to obtain a solid-liquid mixture;
and carrying out solid-liquid separation on the solid-liquid mixture, and sequentially washing, drying and calcining the obtained solid to obtain the SDC component.
The method mixes the cerous nitrate, the samarium nitrate and water to obtain the cerium-samarium mixed solution. In the invention, the concentration of total metal ions in the cerium-samarium mixed solution is preferably 0.5-2 mol/L, more preferably 0.8-1.7 mol/L, and still more preferably 1-1.5 mol/L. In the present invention, the molar ratio of the cerium nitrate to the samarium nitrate is preferably 4: 1. in the present invention, the water is preferably deionized water.
After the mixed solution of cerium-samarium is obtained, the sodium carbonate solution is added into the mixed solution, stirred and then kept stand to obtain a solid-liquid mixture. In the invention, the concentration of the sodium carbonate solution is preferably 0.5-2 mol/L, more preferably 0.8-1.7 mol/L, and still more preferably 1-1.5 mol/L. In the present invention, the molar ratio of the total metal ions in the cerium-samarium mixed solution to the carbonate in the sodium carbonate solution is preferably 1: (1.2 to 2.5), more preferably 1: (1.4-2.3), and more preferably 1: (1.6-2.1). In the present invention, the manner of adding the sodium carbonate solution to the mixed solution is preferably dropwise; the dripping speed is preferably 2-5 drops/s, and more preferably 3-4 drops/s. In the present invention, the dropping is preferably performed under stirring; the stirring is not particularly limited in the present invention, and a stirring known to those skilled in the art may be employed.
After the sodium carbonate solution and the cerium-samarium mixed solution are mixed, the obtained mixed system is stirred and then stands to obtain a solid-liquid mixture. In the invention, the stirring time is 1-5 h; the stirring rate is not particularly limited in the present invention, and a stirring rate known to those skilled in the art may be used. In the invention, the standing time is preferably 6-20 h, more preferably 8-18 h, and still more preferably 10-15 h. According to the invention, the sodium carbonate solution and the cerium-samarium mixed solution are favorably fully mixed for precipitation reaction by standing, the completeness of the precipitation reaction is increased, and the solid-liquid separation effect in the later stage is improved.
After a solid-liquid mixture is obtained, the solid-liquid mixture is subjected to solid-liquid separation, and the obtained solid is sequentially washed, dried and calcined to obtain the SDC component. In the present invention, the particle size of the SDC component is preferably 50 to 200 nm.
The solid-liquid separation mode is not particularly limited in the invention, and a solid-liquid separation mode known to those skilled in the art can be adopted, specifically, such as suction filtration. In the invention, the pH value of the washed product is preferably 7-8, more preferably 7-7.8, and still more preferably 7-7.5. After washing, the invention gives a white precipitate.
In the invention, the drying temperature is preferably 100-150 ℃, more preferably 110-140 ℃, and further preferably 120-130 ℃; the time is preferably 6 to 20 hours, more preferably 8 to 18 hours, and still more preferably 10 to 16 hours. In the present invention, the drying device is preferably a drying oven.
In the invention, the calcination temperature is preferably 750-900 ℃, more preferably 770-880 ℃, and still more preferably 800-850 ℃; the time is preferably 3 to 6 hours, more preferably 3.5 to 5.5 hours, and still more preferably 4 to 5 hours. In the present invention, the calcination apparatus is preferably a muffle furnace. The invention is beneficial to removing oxides generated by the decomposition of raw material substances through calcination, and simultaneously removes impurities through decomposition to obtain pure-phase SDC components.
In the present invention, the NACL component is preferably a commercially available product. In embodiments of the present invention, the NACL component is preferably purchased from Tianjin Baumo technologies.
In the present invention, the preparation method of the LST-SDC-NCAL composite material preferably comprises the steps of:
and mixing the LST component, the SDC component and the NCAL component to obtain the LST-SDC-NCAL composite material.
In the present invention, the mass ratio of the LST component, SDC component and NCAL component is preferably 3:4: 3. the mixing is not particularly limited in the present invention, and may be performed by a method known to those skilled in the art.
The invention also provides application of the LST-SDC-NCAL composite material in the technical scheme in a solid oxide fuel cell, and the LST-SDC-NCAL composite material is used as an anode, a solid electrolyte and a cathode of the solid oxide fuel cell.
The invention also provides a single-layer fuel cell, which comprises an anode, a solid electrolyte and a cathode, wherein the cathode and the anode are independently foamed nickel loaded with the LST-SDC-NCAL composite material, and the solid electrolyte is the LST-SDC-NCAL composite material; the LST-SDC-NCAL composite material is the LST-SDC-NCAL composite material in the technical scheme.
The invention also provides a preparation method of the single-layer fuel cell, which comprises the following steps:
mixing the LST-SDC-NCAL composite material with terpineol to obtain slurry;
coating one side of the slurry on the surface of the foamed nickel, and drying to obtain the foamed nickel loaded with the LST-SDC-NCAL composite material;
and sequentially laminating the foamed nickel loaded with the LST-SDC-NCAL composite material, the LST-SDC-NCAL composite material and the foamed nickel loaded with the LST-SDC-NCAL composite material, and pressing to obtain the single-layer fuel cell.
The LST-SDC-NCAL composite material and terpineol are mixed to obtain slurry.
In the present invention, the volume ratio of the LST-SDC-NCAL composite material to terpineol is preferably 1: (2-4), more preferably 1: (2.5-3.5).
After the slurry is obtained, the single side of the slurry is coated on the surface of the foamed nickel, and the foamed nickel loaded with the LST-SDC-NCAL composite material is obtained after drying. The nickel foam is not particularly limited in the present invention, and it is possible to use nickel foam well known to those skilled in the art in the present invention. In the invention, the coating amount of the slurry relative to the surface of the foamed nickel is preferably 0.1-0.3 g/0.64cm2More preferably 0.1 to 0.2g/0.64cm2More preferably 0.1 to 0.15g/0.64cm2. The process of the present invention is not particularly limited and those skilled in the art will be familiar with the application of the coatingCan be applied, in particular, by brushing, knife coating or spraying. In the present invention, the drying temperature is preferably 120 ℃ and the drying time is preferably 0.5 h. The present invention removes terpineol by drying.
After obtaining the foamed nickel loaded with the LST-SDC-NCAL composite material, sequentially laminating the foamed nickel loaded with the LST-SDC-NCAL composite material, the LST-SDC-NCAL composite material and the foamed nickel loaded with the LST-SDC-NCAL composite material, and pressing to obtain the single-layer fuel cell. In the present invention, the mass ratio of the LST-SDC-NCAL composite material as the solid electrolyte to the nickel foam loaded with the LST-SDC-NCAL composite material as the anode is preferably (1 to 3): 1, more preferably (1.5 to 2.5): 1; the mass ratio of the LST-SDC-NCAL composite material as the solid electrolyte to the foamed nickel loaded with the LST-SDC-NCAL composite material as the cathode is preferably (1-3): 1, more preferably (1.5 to 2.5): 1. in the invention, one side of the foamed nickel loaded with the LST-SDC-NCAL composite material, which is coated with the LST-SDC-NCAL composite material, is in contact with the LST-SDC-NCAL composite material serving as a solid electrolyte.
In the invention, the pressing pressure is preferably 100-400 MPa, more preferably 150-350 MPa, and still more preferably 200-300 MPa; the time is preferably 1 to 4min, more preferably 2 to 3min, and most preferably 2 min. In the present invention, the compression apparatus is preferably a tablet press.
To further illustrate the present invention, a LST-SDC-NCAL composite material and its preparation method and use are described in detail below with reference to the examples, which should not be construed as limiting the scope of the invention.
Example 1
Preparation of semiconductor Material LST (La)0.25Sr0.75Ti1O3-δ) The method comprises the following steps:
respectively weighing corresponding lanthanum oxide powder and strontium carbonate powder according to the molecular molar ratio of LST, and stirring and dissolving the lanthanum oxide powder and the strontium carbonate powder into a dilute nitric acid solution to obtain a first mixture; weighing a proper amount of titanium isopropoxide according to the molecular mole ratio of titanium in the chemical composition of LST, and mixing the titanium isopropoxide with the LST in a volume ratio of 1: 4, stirring and dissolving the titanium ions into ethylene glycol, and after uniformly mixing, mixing the titanium ions and the citric acid according to a molar ratio of 1: 4, adding citric acid into the ethylene glycol solution of the titanium isopropoxide to obtain a second mixture; mixing the first mixture and the second mixture, stirring for 12h, and then heating and stirring at 80 ℃ until water is evaporated to form brown gel; placing the obtained gel in a muffle furnace, and preserving heat for 2h at 530 ℃; and taking out the powder, grinding the powder into powder, and sintering the powder in a muffle furnace at 1200 ℃ for 5 hours to obtain a white powdery LST component.
The LST component obtained was observed by scanning electron microscopy, and the SEM image is shown in FIG. 1. As can be seen from FIG. 1, the powder particles of the LST component provided by the invention are uniformly distributed, and the particle size is 20-300 nm.
Preparation of Ionic conductor Material SDC (Ce)0.8Sm0.2O2-x) The method comprises the following steps:
weighing cerium nitrate and samarium nitrate with corresponding mass according to the molar ratio of SDC molecules, dissolving the cerium nitrate and the samarium nitrate into a proper amount of deionized water, and uniformly stirring to prepare a mixed solution with the concentration of total metal ions of 1 mol/L; according to the molar ratio of the total metal ions to the carbonate ions of 1: 2, weighing sodium carbonate according to the proportion, and dissolving the sodium carbonate in deionized water, wherein the concentration of the sodium carbonate solution is 1 mol/L; dropping a sodium carbonate solution into the mixed solution at the speed of 3 drops/s, ensuring that the mixed solution is in a continuous stirring state in the process, continuously stirring for 4 hours, and standing for 12 hours to obtain a solid-liquid mixture; and carrying out suction filtration on the obtained solid-liquid mixture, washing the white solid substance obtained by suction filtration for multiple times until the pH value is 7-8, then putting the obtained white precipitate into a drying box, drying for 12 hours at 120 ℃, and finally putting the dried product into a muffle furnace, and sintering for 4 hours at 800 ℃ to obtain the SDC component.
The SDC component obtained is observed by a scanning electron microscope, and the SEM image is shown in figure 2. As can be seen from figure 2, the powder particles of the SDC component provided by the invention are uniformly distributed, and the particle size is 50-200 nm.
By the purchase of Ni from Tianjin Bamo technology0.8Co0.15Al0.05LiO2-yIs a NCAL component. The purchased NCAL component was observed by scanning electron microscopy and the SEM image obtained is shown in FIG. 3. From FIG. 3, it can be seenThe powder particles of the NCAL component are uniformly distributed.
After obtaining the LST component and the SDC component, mixing the LST component, the SDC component and the NCAL component according to the mass ratio of 3:4:3 to obtain mixed powder; taking terpineol according to 3 times of the volume of the powder, and uniformly mixing the terpineol with the mixed powder to obtain slurry; 0.1g of the slurry was coated on 0.64cm2Obtaining the coating foam nickel on the surface of the foam nickel; and weighing 0.3g of mixed powder as electrolyte, adding foamed nickel coated with the mixed powder on two sides, and performing compression molding by using a tablet press under 200MPa to obtain the LST-SDC-NCAL composite material.
XRD testing was performed on the LST component, SDC component, NCAL component and LST-SDC-NCAL composite, and the resulting XRD pattern is shown in FIG. 4. As can be seen from FIG. 4, CeO was contained in the LST component2Is fluorite structure, NCAL is lamellar structure, LST is perovskite structure; each material presents an obvious diffraction peak, and other miscellaneous peaks are not observed, which indicates that the LST component and SDC component materials obtained by experimental preparation are pure phases; the three-phase materials do not react with each other, and other impurities cannot be generated.
Test example 1
The LST-SDC-NCAL composite obtained in example 1 was used as a single layer fuel cell.
The resulting single layer fuel cell was subjected to the following performance tests:
1. I-V test and I-P test, the test method is as follows: and (3) mounting the cell on a test fixture, placing the cell in a test furnace at 550 ℃, pre-sintering for 30min, and introducing hydrogen and air to the two sides of the cell respectively. And meanwhile, the IT8511 electronic load is used for testing and recording the performance data of the battery in real time.
The resulting I-V curve and I-P curve are shown in FIG. 5. As can be seen from FIG. 5, the single layer fuel cell has an open circuit voltage higher than 1V and a power density of 222mW cm at a test temperature of 550 deg.C-2It was confirmed that the single layer fuel cell provided did not short-circuit and achieved considerable output performance. As the test temperature decreases, the electrical performance of the single layer fuel cell decreases, which is caused by the decrease in the catalytic activity of the material with decreasing temperature.
2. Electrochemical impedance spectroscopy test, the test method is as follows: the test was carried out using an electrochemical workstation GamryReference3000 at an operating temperature of 550 c with hydrogen and air supplied to both sides of the cell.
The EIS map of the resulting single layer fuel cell is shown in fig. 6. As can be seen from fig. 6, the ohmic resistance of the single-layer fuel cell increases and the low-frequency arc resistance tends to increase with decreasing temperature.
3. And (3) testing the stability, wherein the testing method comprises the following steps: after the I-V curve and the I-P curve are measured, the current density is set to be constant at 100mA/cm, the battery is allowed to continuously output and discharge, and meanwhile, test data are recorded.
The resulting stability test pattern is shown in FIG. 7. As can be seen from FIG. 7, the battery has a continuous discharge time of more than 65h and a relatively stable performance output, and the single-layer fuel cell provided by the invention has good stability and does not generate an obvious layering phenomenon.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method of making a single layer fuel cell, comprising the steps of:
mixing the LST-SDC-NCAL composite material with terpineol to obtain slurry;
coating one side of the slurry on the surface of the foamed nickel, and drying to obtain the foamed nickel loaded with the LST-SDC-NCAL composite material;
sequentially laminating and pressing the foamed nickel loaded with the LST-SDC-NCAL composite material, the LST-SDC-NCAL composite material and the foamed nickel loaded with the LST-SDC-NCAL composite material to obtain the single-layer fuel cell;
the LST-SDC-NCAL composite comprises a LST component, a SDC component and a NCAL component which are uniformly mixed; the mass ratio of the LST component to the SDC component to the NCAL component is (1-5): (3-5): (1-5);
the LST component has a chemical composition of La0.25Sr0.75Ti1O3-δThe chemical composition of the SDC component is Ce0.8Sm0.2O2-xThe chemical composition of the NCAL component is Ni0.8Co0.15Al0.05LiO2-yδ, x and y are values that keep the compound electrically neutral;
the LST component has a particle size of 20-300 nm, and the SDC component has a particle size of 50-200 nm.
2. The method of making according to claim 1, wherein the LST component is made by a method comprising the steps of:
mixing lanthanum oxide, strontium carbonate and nitric acid to obtain a first mixture;
mixing a glycol solution of titanium isopropoxide with citric acid to obtain a second mixture;
and mixing the first mixture and the second mixture, and then sequentially carrying out first heating and heat preservation, heating and then carrying out second heating and heat preservation, grinding and sintering to obtain the LST component.
3. The method according to claim 2, wherein the volume ratio of titanium isopropoxide to ethylene glycol in the ethylene glycol solution of titanium isopropoxide is 1: (2-8); the molar ratio of the ethylene glycol solution of titanium isopropoxide to citric acid is 1: (1-6).
4. The preparation method according to claim 2, wherein the first mixture and the second mixture are mixed for 8 to 20 hours;
the temperature of the first heating and heat preservation is 50-90 ℃, and the time is based on the obtained gel;
the temperature of the second heating and heat preservation is 400-600 ℃, and the time is 1.5-4 hours;
the sintering temperature is 1100-1300 ℃, and the sintering time is 4-7 h.
5. A method of making the SDC component of claim 1, wherein the SDC component is made by a method comprising:
mixing cerium nitrate, samarium nitrate and water to obtain a cerium-samarium mixed solution;
adding a sodium carbonate solution into the cerium-samarium mixed solution, stirring and standing to obtain a solid-liquid mixture;
and carrying out solid-liquid separation on the solid-liquid mixture, and sequentially washing, drying and calcining the obtained solid to obtain the SDC component.
6. The preparation method according to claim 5, wherein the concentration of total metal ions in the cerium-samarium mixed solution is 0.5 to 2 mol/L; the concentration of the sodium carbonate solution is 0.5-2 mol/L;
the molar ratio of total metal ions in the cerium-samarium mixed solution to carbonate in the sodium carbonate solution is 1: (1.2-2.5).
7. The preparation method according to claim 5, wherein the stirring time is 1-5 hours; the standing time is 6-20 h; the pH value of the washed product is 7-8;
the drying temperature is 100-150 ℃, and the drying time is 6-20 h;
the calcining temperature is 750-900 ℃, and the time is 3-6 h.
8. A single layer fuel cell comprising an anode, a solid electrolyte and a cathode, wherein the cathode and anode are independently foamed nickel loaded with a LST-SDC-NCAL composite and the solid electrolyte is a LST-SDC-NCAL composite; the LST-SDC-NCAL composite material is the LST-SDC-NCAL composite material in the preparation method of any one of claims 1 to 7.
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