CN112687886A - Intermediate-temperature solid oxide fuel cell composite cathode and preparation method thereof - Google Patents
Intermediate-temperature solid oxide fuel cell composite cathode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite cathode of an intermediate-temperature solid oxide fuel cell and a preparation method thereof. The compound cathode is formed by La0.6Sr0.4Co0.2Fe0.8O3‑δAnd LaSrCo0.2Fe0.8O4‑δThe two materials are compounded. The preparation method comprises the following steps: preparing a cation solution containing La, Sr, Co and Fe ions according to a molecular formula; adding a precipitator into the cationic solution for reaction, aging, filtering, washing, drying in an oven, sieving and calcining the obtained precipitation solution to obtain SP and RP powder; the powder is ball-milled, coated on two sides of an SDC electrolyte thin sheet and then calcined. The obtained yinThe impedance is basically stabilized at 0.1 omega cm within 100h when the electrode works under an open circuit at 750 DEG C2The preparation cost and the impedance of the composite cathode material are reduced, and the composite cathode material has high stability.
Description
Technical Field
The invention relates to a preparation method of a high-performance composite cathode material for a medium-temperature solid oxide fuel cell, belonging to the field of solid oxide fuel cell preparation.
Background
A Solid Oxide Fuel Cell (SOFC) is an all-Solid-state chemical power generation device that directly converts chemical energy stored in Fuel and oxidant into electrical energy at medium and high temperatures with high efficiency and environmental friendliness. Since electrodes tend to suffer from sintering at high temperatures, research on SOFCs in recent years has focused on reducing the operating temperature to an intermediate temperature (600 ℃ C. and 800 ℃ C.) to improve service life. However, conventional cathode materials for SOFCs have poor activity for electrochemically reducing oxygen at intermediate temperatures and the overall efficiency of the cell is low. This is due to the larger radius of the alkaline earth cations, such as Sr, at the A site of the perovskite2+、Ba2+、Pb2+And the like are easy to segregate and precipitate in the form of oxides in the initial perovskite lattice, the formed second phase has poor conductivity, the electron transfer is blocked, the oxygen hole concentration of the electrode surface and the heterogeneous interface is reduced, and the oxygen reaction efficiency is seriously damaged.
In order to inhibit the harmful segregation at the A site of the perovskite structure material, a cathode material compounded by SP and RP phases needs to be prepared. At present, the preparation method of the cathode material of the solid oxide fuel cell has the approaches of solid phase synthesis, PLD (programmable logic device) film preparation and the like. Although the SP-RP composite film structure prepared by the PLD method can enhance the exchange kinetics (nearly 2 orders of magnitude) of the electrode surface and activate the electron transfer at the interface, the stability of the electrode is greatly improved, but the equipment is expensive and is difficult to use in a large scale. The composite electrode is prepared by directly mixing SP and RP by a solid phase method, so that two phases are difficult to disperse uniformly and easy to aggregate, an expected nano structure and an ideal heterogeneous interface are difficult to form, and the transmission of oxygen ions and electrons in an electrode body is hindered.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the problem that SP and RP are dispersed unevenly in the existing solid phase method to block the transmission of oxygen ions and electrons is solved.
In order to solve the technical problem, the invention provides a composite cathode of an intermediate-temperature solid oxide fuel cell, which is characterized in that the composite cathode is formed by La molecular formulas0.6Sr0.4Co0.2Fe0.8O3-δAnd LaSrCo0.2Fe0.8O4-δThe two materials are compounded.
The invention also provides a preparation method of the intermediate-temperature solid oxide fuel cell composite cathode, which is characterized by comprising the following steps:
step 1): according to the formula La0.6Sr0.4Co0.2Fe0.8O3-δAnd LaSrCo0.2Fe0.8O4-δPreparing a cation solution containing La, Sr, Co and Fe ions;
step 2): dropwise adding a mixed solution of ammonium bicarbonate and ammonia water serving as a precipitator into the cationic solution for reaction, and stirring continuously during the reaction until the reaction is complete to obtain a precipitation solution;
step 3): aging, filtering, washing and drying in an oven the precipitate solution obtained in the step 2), sieving, and calcining in a muffle furnace to obtain SP and RP powder;
step 4): putting the SP powder and the RP powder obtained in the step 3) into a ball milling tank for ball milling;
step 5): and coating black slurry obtained by ball milling on two sides of the SDC electrolyte sheet, and then calcining to obtain the intermediate-temperature solid oxide fuel cell composite cathode.
Preferably, the step 1) specifically comprises: in La (NO)3)3、Sr(NO3)2、Co(NO3)2、Fe(NO3)3Deionized water is added to prepare cationic solutions with the concentrations of 0.4mol/L, 1.2mol/L and 0.4mol/L respectively.
Preferably, the concentration of the precipitant in the step 2) is 2mol/L, and the reaction time is 50-70 min.
Preferably, the aging time in the step 3) is 30-60 min; the washing adopts suction filtration, and the washing is carried out for 3 times by using deionized water and then 1 time by using absolute ethyl alcohol; the drying time of the oven is 24-48 h; the calcination temperature is 1000 ℃ and the calcination time is 2 h.
Preferably, the ball mill body in the step 4) comprises: putting the powder into a ball milling tank, adding ball milling beads, and injecting PMMA and terpineol for ball milling.
Preferably, the SDC electrolyte sheet in step 5) is prepared by mixing Ce0.8Sm0.2O1.9And (3) tabletting the powder, and placing the powder in a muffle furnace for heat preservation at 1500 ℃ for 5h to obtain the compact SDC electrolyte.
Preferably, the calcining temperature in the step 5) is 900 ℃ and the time is 2 h.
Preferably, the coating in the step 5) is performed by screen printing.
The invention provides a preparation method of a high-performance composite cathode for a solid oxide fuel cell, aiming at the problems that PLD (pulsed laser deposition) equipment is expensive, the yield is low, and large-scale application is difficult to realize and the like. The method adopts a coprecipitation method to obtain the SP and RP nano pure-phase powder with less monodispersion and agglomeration, and prepares the SP-RP composite cathode through mixing and screen printing, the obtained impedance is 0.05 times of that of the solid-phase reaction method electrode under the same condition, and the electrode performance of the SOFC is greatly improved.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the high-performance composite cathode for the solid oxide fuel cell, the SP and RP pure-phase nano powder is prepared by adopting a coprecipitation method, and the composite cathode for the solid oxide fuel cell is obtained by simple mechanical mixing and screen printing processes. The method solves the process problem that the battery efficiency is influenced by two-phase agglomeration caused by uneven powder particles and poor dispersibility.
Further, according to the preparation method of the high-performance composite cathode for the solid oxide fuel cell, the pure-phase SP and RP precursor powder can be calcined at 1000 ℃ to obtain monodisperse nano-scale powder, the average grain size is about 150-200 nm, and the preparation method is advantageous in uniformity and dispersibility of the powder.
Furthermore, according to the preparation method of the high-performance composite cathode for the solid oxide fuel cell, the process of the coprecipitation method for preparing the perovskite structure nano powder is simple, complex process conditions such as solid-phase ball milling and pulse laser deposition are not needed, the powder can be obtained through synthesis and calcination at room temperature, and the preparation method is suitable for large-scale production.
Further, according to the preparation method of the high-performance composite cathode for the solid oxide fuel cell, the single-phase SP and RP nano powder prepared by adopting the coprecipitation process can be prepared into a cathode material with better performance according to a certain proportion only by simple physical mixing. Can obviously improve the oxygen surface exchange efficiency (ORR), which has important significance for improving the electrochemical performance of the SOFCs.
Drawings
FIG. 1 is XRD patterns of a pure SP phase prepared in example 1, a pure RP phase prepared in example 3, and a mixed SP and RP nanopowder prepared in example 3;
FIG. 2 is a graph of the polarization impedance of symmetric half-cells at 700 ℃ and 800 ℃ for CP-SP, CP-RP and 90% CP-SP electrode materials respectively prepared by co-precipitation in examples 1-3;
FIG. 3 shows the result of the operation stability test of the cathode material prepared in example 3 at 750 ℃ under an open circuit;
FIG. 4 is a diagram of the polarization impedance of symmetric half-cells of SSR-SP, SSR-RP and 90% SSR-SP electrode materials prepared by solid phase method in example 4 at 700 deg.C and 800 deg.C, respectively;
FIG. 5 is a scanning electron microscope image of the micro-morphology of perovskite powder prepared by different methods in examples 3 and 4.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Each raw material used in each example was a commercially available product.
In the invention, LSCF is SP: la0.6Sr0.4Co0.2Fe0.8O3-δ(ii) a LSCF is RP: LaSrCo0.2Fe0.8O4-δ(ii) a And (3) CP: coprecipitation method (Co-precipitation); SSR: solid phase Reaction (Solid State Reaction).
The phase structure test used in the examples of the present invention employed an X-ray diffractometer (XRD) with the instrument model D/Max-2200PC, Rigaku, Japan, under the following test conditions: the radiation of the CuK alpha rays is,
the voltage and the current of the instrument are respectively 40kV and 200mA, and the 2 theta scanning range is 10-80 degrees;
the appearance observation is carried out by adopting a Field Emission Scanning Electron Microscope (FESEM), and the model of the apparatus is JSM-6700F, Tokyo, Japan;
cell impedance testing A symmetrical half cell at 5% H using an electrochemical workstation model Zahner IM6eX2Ac impedance tests were performed under Ar atmosphere, air atmosphere and wet hydrogen atmosphere. The test conditions were: the amplitude of the voltage amplification signal is 10mV, and the frequency range is 1 MHz-0.01 Hz. The data are tested at a temperature of 600-900 ℃ in a reducing atmosphere every 50 ℃. And testing the data at the temperature of 600-800 ℃ every 50 ℃ in an oxidizing atmosphere.
Example 1
A preparation method of a cathode of an intermediate-temperature solid oxide fuel cell comprises the following specific steps:
1. preparing SP:
(1) a commercially available lanthanum nitrate (La (NO) having a purity of 99.9% was used3)3) Strontium nitrate (Sr (NO))3)2) Cobalt nitrate (Co (NO)3)2) And iron nitrate (Fe (NO)3)3) To reactDissolving the raw materials in deionized water, stirring to obtain solutions of 0.4mol/L, 1.2mol/L, and 0.4mol/L, respectively, determining the concentration of each metal ion by chemical analysis, and preparing into La solution of the formula0.6Sr0.4Co0.2Fe0.8O3-δPouring 37.50mL, 8.33mL, 12.50mL and 50.00mL of four metal ion salt solutions into a 500mL beaker according to the sequence, uniformly mixing to obtain a mixed solution, and adding deionized water to 250mL to obtain a mother solution with the metal ion concentration of 0.1 mol/L;
(2) 150mL of a precipitant (a mixed solution of ammonium hydrogencarbonate and aqueous ammonia) having a concentration of 2mol/L was dropped into the mother liquor at a rate of 4mL/min and sufficiently stirred. Continuing stirring for 3 minutes until the precipitant is dripped off, stopping stirring, and aging the stirred precipitate at room temperature of 25 ℃ for 30 min;
(3) washing the obtained precipitate with deionized water for three times and absolute ethyl alcohol for two times, drying the washed precipitate in an oven at 60 ℃ for 24 hours, and sieving the dried powder in a 200-mesh sieve to obtain precursor powder. And (3) keeping the temperature of the precursor powder in the air at 1000 ℃ for 2h in a muffle furnace, and calcining to obtain the SP nano powder.
(4) Washing the obtained precipitate with deionized water for three times and absolute ethyl alcohol for two times, drying the washed precipitate in an oven at 60 ℃ for 24 hours, and sieving the dried powder in a 200-mesh sieve to obtain precursor powder. And (3) keeping the temperature of the precursor powder in the air at 1000 ℃ for 2h in a muffle furnace, and calcining to obtain the RP nano powder.
2. Preparing a battery:
weighing SDC (Ce)0.8Sm0.2O1.9) And putting the powder tablets in a muffle furnace, heating to 1500 ℃, keeping the temperature for 5 hours to obtain a compact SDC electrolyte, putting SP powder obtained by a wet coprecipitation method into a ball milling tank, adding ball milling beads, injecting a small amount of PMMA and terpineol for ball milling, coating the obtained black slurry on two sides of an SDC electrolyte sheet by a screen printing method, and calcining at 900 ℃ for 2 hours to obtain the LSCF/SDC/LSCF symmetrical half cell.
Example 2
A preparation method of a cathode of an intermediate-temperature solid oxide fuel cell comprises the following specific steps:
1. preparing RP:
(1) a commercially available lanthanum nitrate (La (NO) having a purity of 99.9% was used3)3) Strontium nitrate (Sr (NO))3)2) Cobalt nitrate (Co (NO)3)2) And iron nitrate (Fe (NO)3)3) Dissolving the reaction raw materials in deionized water, stirring to obtain solutions of 0.4mol/L, 1.2mol/L and 0.4mol/L, respectively, determining the concentration of each metal ion by chemical analysis, and preparing into La solution of the formula0.6Sr0.4Co0.2Fe0.8O3-δRespectively taking 62.50mL, 20.83mL, 12.50mL and 50.00mL of four metal ion salt solutions in sequence, pouring the four metal ion salt solutions into a 500mL beaker, uniformly mixing the four metal ion salt solutions to obtain a mixed solution, and adding deionized water to 250mL to obtain a mother solution with the metal ion concentration of 0.1 mol/L;
(2) 150mL of a precipitant (a mixed solution of ammonium hydrogencarbonate and aqueous ammonia) having a concentration of 2mol/L was dropped into the mother liquor at a rate of 4mL/min and sufficiently stirred. Continuing stirring for 3 minutes until the precipitant is dripped off, stopping stirring, and aging the stirred precipitate at room temperature of 25 ℃ for 30 min;
(3) washing the obtained precipitate with deionized water for three times and absolute ethyl alcohol for two times, drying the washed precipitate in an oven at 60 ℃ for 24 hours, and sieving the dried powder in a 200-mesh sieve to obtain precursor powder. And (3) keeping the temperature of the precursor powder in the air at 1000 ℃ for 2h in a muffle furnace, and calcining to obtain the RP nano powder.
2. Preparing a battery:
weighing SDC (Ce)0.8Sm0.2O1.9) And (2) placing the powder tablets in a muffle furnace, heating to 1500 ℃, keeping the temperature for 5 hours to obtain a compact SDC electrolyte, placing RP powder obtained by a wet coprecipitation method in a ball milling tank, adding ball milling beads, injecting a small amount of PMMA (polymethyl methacrylate) and terpineol for ball milling, coating the obtained black slurry on two sides of an SDC electrolyte sheet by a screen printing method, and calcining at 900 ℃ for 2 hours to obtain the LSCF/SDC/LSCF symmetrical half cell.
Example 3
A preparation method of a composite cathode of an intermediate-temperature solid oxide fuel cell comprises the following specific steps:
1. preparing SP:
(1) a commercially available lanthanum nitrate (La (NO) having a purity of 99.9% was used3)3) Strontium nitrate (Sr (NO))3)2) Cobalt nitrate (Co (NO)3)2) And iron nitrate (Fe (NO)3)3) Dissolving the reaction raw materials in deionized water, stirring to obtain solutions of 0.4mol/L, 1.2mol/L and 0.4mol/L, respectively, determining the concentration of each metal ion by chemical analysis, and preparing into La solution of the formula0.6Sr0.4Co0.2Fe0.8O3-δPouring 37.50mL, 8.33mL, 12.50mL and 50.00mL of four metal ion salt solutions into a 500mL beaker according to the sequence, uniformly mixing to obtain a mixed solution, and adding deionized water to 250mL to obtain a mother solution with the metal ion concentration of 0.1 mol/L;
(2) 150mL of a precipitant (a mixed solution of ammonium hydrogencarbonate and aqueous ammonia) having a concentration of 2mol/L was dropped into the mother liquor at a rate of 4mL/min and sufficiently stirred. Continuing stirring for 3 minutes until the precipitant is dripped off, stopping stirring, and aging the stirred precipitate at room temperature of 25 ℃ for 30 min;
(3) washing the obtained precipitate with deionized water for three times and absolute ethyl alcohol for two times, drying the washed precipitate in an oven at 60 ℃ for 24 hours, and sieving the dried powder in a 200-mesh sieve to obtain precursor powder. And (3) keeping the temperature of the precursor powder in the air at 1000 ℃ for 2h in a muffle furnace, and calcining to obtain the SP nano powder.
2. Preparing RP:
(1) a commercially available lanthanum nitrate (La (NO) having a purity of 99.9% was used3)3) Strontium nitrate (Sr (NO))3)2) Cobalt nitrate (Co (NO)3)2) And iron nitrate (Fe (NO)3)3) Dissolving the reaction raw materials in deionized water, stirring to obtain solutions of 0.4mol/L, 1.2mol/L and 0.4mol/L, respectively, determining the concentration of each metal ion by chemical analysis, and preparing into La solution of the formula0.6Sr0.4Co0.2Fe0.8O3-δFour metal ion salt solutions in orderRespectively pouring 62.50mL, 20.83mL, 12.50mL and 50.00mL into a 500mL beaker, uniformly mixing to obtain a mixed solution, and adding deionized water to 250mL to obtain a mother solution with the metal ion concentration of 0.1 mol/L;
(2) 150mL of a precipitant (a mixed solution of ammonium hydrogencarbonate and aqueous ammonia) having a concentration of 2mol/L was dropped into the mother liquor at a rate of 4mL/min and sufficiently stirred. Continuing stirring for 3 minutes until the precipitant is dripped off, stopping stirring, and aging the stirred precipitate at room temperature of 25 ℃ for 30 min;
(3) washing the obtained precipitate with deionized water for three times and absolute ethyl alcohol for two times, drying the washed precipitate in an oven at 60 ℃ for 24 hours, and sieving the dried powder in a 200-mesh sieve to obtain precursor powder. And (3) keeping the temperature of the precursor powder in the air at 1000 ℃ for 2h in a muffle furnace, and calcining to obtain the RP nano powder.
3. Preparing a battery:
weighing SDC (Ce)0.8Sm0.2O1.9) And putting the powder tablets in a muffle furnace, heating to 1500 ℃, keeping the temperature for 5 hours to obtain a compact SDC electrolyte, putting SP and RP obtained by a coprecipitation method into a ball milling tank according to the mass ratio of 9:1, adding ball milling beads, injecting a small amount of PMMA and terpineol for ball milling, coating the obtained black slurry on two sides of the SDC electrolyte sheet by a screen printing method, and calcining for 2 hours at 900 ℃ to obtain the LSCF/SDC/LSCF symmetrical half cell.
FIG. 1 is the XRD patterns of SP and RP nanopowders in example 1 above. Through analysis, the crystal structures of two kinds of powder obtained after the precursor is calcined for 2 hours at 1000 ℃ in the air atmosphere are respectively single perovskite structure LaFeO3Type (JCPDS #75-0439, SLF113, space group 167: R-3c) and layered perovskite phase structure SrLaFeO4Form (JCPDS #71-1745, SLF214, space group 139: I4/mmm), no hetero-phase peak was observed. The two materials are mechanically mixed according to the mass ratio of 9:1, and the XRD pattern of the obtained powder has obvious SP and RP diffraction peaks, which shows that two phases coexist after SP and RP are mechanically mixed.
FIG. 2 shows symmetrical half-cells of CP-SP, CP-RP and 90% CP-SP electrode materials prepared by coprecipitation method in example 1 above at 700 deg.C and 800 deg.C, respectivelyPolarization impedance plot. The polarization impedance of the CP-SP symmetrical half cell is 0.422 omega cm at 700 ℃ and 800 ℃ respectively2And 0.089. omega. cm2The polarization impedance of the 90% CP-SP symmetric half cell is 0.244 omega cm at 700 ℃ and 800 ℃ respectively2And 0.060. omega. cm2The impedance is obviously lower than that of CP-SP, and the impedance is reduced by half especially at the medium temperature of 700 ℃. This shows that the mixing of the two phases SP and RP in a certain ratio can reduce the impedance.
FIG. 3 shows the changes of the CP-SP powder and CP-RP powder prepared in example 1 of the present invention with respect to the resistance with time when they are operated at 750 ℃ for 100 hours. It can be seen from the graph that the impedance is substantially stable within 100h (0.1. omega. cm)2) The test result is superior to the cathode report on LSCF by Francisco et al in JECS journal in 2019 (0.33 omega cm)2750 deg.C) and is superior to previously reported LSCF electrodes. This indicates that the powders prepared by the coprecipitation method used in the present invention have good stability.
Example 4
A method for preparing a composite cathode of a solid oxide fuel cell by a solid phase method comprises the following specific steps:
1. preparing SP:
(1) according to single phase perovskite La0.6Sr0.4Co0.2Fe0.8O3-δSynthesizing 0.1mol of SP, and weighing 9.77g of La respectively2O3、5.91g SrCO3、3.32g Co2O3、6.39g Fe2O3Adding a small amount of absolute ethyl alcohol into the powder, then ball-milling for 18h at the rotating speed of 350rd/min, drying and briquetting;
(2) and (3) preserving the temperature of the pressed block in a muffle furnace at 1000 ℃ for 5 hours, and grinding and sieving to obtain SP powder.
2. Preparing RP:
(1) LaSrCo based on layered perovskite structure0.2Fe0.8O4-δIn a stoichiometric ratio of 16.2gLa, respectively2O3、14.76gSrCO3、3.32g Co2O3、6.39gFe2O3Adding a small amount of absolute ethyl alcohol into the powder, then ball-milling for 18h at the rotating speed of 350rd/min, drying and briquetting;
(2) and (3) preserving the temperature of the pressed block in a muffle furnace at 1000 ℃ for 5 hours, and grinding and sieving to obtain the RP powder.
3. Preparing a battery:
weighing SDC powder tablets, placing the SDC powder tablets in a muffle furnace, heating to 1500 ℃, preserving heat for 5 hours to obtain compact SDC electrolyte, putting SP and RP obtained by a solid phase method into a ball milling tank according to the mass ratio of 9:1 and 2g of powder in total mass, adding ball milling beads, injecting a small amount of PMMA (polymethyl methacrylate), performing ball milling by terpineol, coating obtained black slurry on two sides of an SDC electrolyte sheet by a screen printing method, and calcining for 2 hours at 900 ℃ to obtain the LSCF/SDC/LSCF symmetrical half cell. The impedance of the final composite powder was instead higher than that of the pure SP powder, as shown in fig. 3. The SP and the RP prepared by the coprecipitation method can reduce the impedance of the composite powder only by simple mechanical mixing.
FIG. 4 is a graph of the polarization impedance of symmetric half-cells at 700 deg.C and 800 deg.C for SSR-SP, SSR-RP and 90% SSR-SP electrode materials prepared by solid phase method in example 4 of this invention. The polarization impedance of the SSR-RP symmetrical half cell is 4.669 omega cm at 700 ℃ and 800 ℃ respectively2And 0.845. omega. cm2The polarization impedance of 90% SSR-SP symmetrical half cell is 8.626 omega cm at 700 ℃ and 800 ℃ respectively2And 1.1326 Ω cm2The impedance is obviously higher than CP-SP, and is opposite to the impedance of a cathode electrode prepared by perovskite powder obtained by a coprecipitation method, and the polarization impedance of a symmetrical half cell after mechanical mixing by a solid phase method (90% SSR-SP) is higher than that of a symmetrical half cell of single-phase perovskite. The powder prepared by the solid phase method has poor dispersibility and easy agglomeration, but blocks the transmission of cathode oxygen ions, and the powder prepared by the coprecipitation method is nano-scale, has good dispersibility and high activity, and is beneficial to forming an SP-RP heterogeneous interface by mechanical mixing.
FIG. 5 is a scanning electron microscope image of the micro-morphology of perovskite powder prepared by different methods in example 3. The calcination temperature for all samples was 1000 ℃ for 2 h. In fig. 5, a-c are scanning electron micrographs of SP, RP and SP: RP ═ 9:1 samples prepared using the coprecipitation method (CP), and it can be seen that the particle size of the powder is uniform; compared with the perovskite powder prepared by the co-precipitation method of a-c in the figure 5, the perovskite nano powder obtained by the d-f solid phase method (SSR) in the figure 5 has serious agglomeration and uneven dispersion and is of a polygonal structure. This shows that the nano powder prepared by coprecipitation method has high activity and good performance.
Claims (9)
1. The composite cathode of the intermediate-temperature solid oxide fuel cell is characterized by comprising the following components of which the molecular formulas are La respectively0.6Sr0.4Co0.2Fe0.8O3-δAnd LaSrCo0.2Fe0.8O4-δThe two materials are compounded.
2. A method for preparing a composite cathode of an intermediate-temperature solid oxide fuel cell according to claim 1, characterized by comprising the following steps:
step 1): according to the formula La0.6Sr0.4Co0.2Fe0.8O3-δAnd LaSrCo0.2Fe0.8O4-δPreparing a cation solution containing La, Sr, Co and Fe ions;
step 2): dropwise adding a mixed solution of ammonium bicarbonate and ammonia water serving as a precipitator into the cationic solution for reaction, and stirring continuously during the reaction until the reaction is complete to obtain a precipitation solution;
step 3): aging, filtering, washing and drying in an oven the precipitate solution obtained in the step 2), sieving, and calcining in a muffle furnace to obtain SP and RP powder;
step 4): putting the SP powder and the RP powder obtained in the step 3) into a ball milling tank for ball milling;
step 5): and coating black slurry obtained by ball milling on two sides of the SDC electrolyte sheet, and then calcining to obtain the intermediate-temperature solid oxide fuel cell composite cathode.
3. A method for preparing a composite cathode of an intermediate-temperature solid oxide fuel cell according to claim 2, wherein the step 1) specifically comprises: in La (NO)3)3、Sr(NO3)2、Co(NO3)2、Fe(NO3)3Deionized water is added to prepare cationic solutions with the concentrations of 0.4mol/L, 1.2mol/L and 0.4mol/L respectively.
4. The preparation method of the intermediate-temperature solid oxide fuel cell composite cathode according to claim 2, wherein the concentration of the precipitant in the step 2) is 2mol/L, and the reaction time is 50-70 min.
5. A method for preparing a composite cathode of an intermediate-temperature solid oxide fuel cell according to claim 2, wherein the aging time in the step 3) is 30-60 min; the washing adopts suction filtration, and the washing is carried out for 3 times by using deionized water and then 1 time by using absolute ethyl alcohol; the drying time of the oven is 24-48 h; the calcination temperature is 1000 ℃ and the calcination time is 2 h.
6. A method for preparing a composite cathode of an intermediate-temperature solid oxide fuel cell according to claim 2, wherein the ball grinding tool body in the step 4) comprises: putting the powder into a ball milling tank, adding ball milling beads, and injecting PMMA and terpineol for ball milling.
7. A method for preparing a composite cathode of an intermediate-temperature solid oxide fuel cell according to claim 2, wherein the SDC electrolyte sheet in the step 5) is prepared by mixing Ce with a solvent0.8Sm0.2O1.9And (3) tabletting the powder, and placing the powder in a muffle furnace for heat preservation at 1500 ℃ for 5h to obtain the compact SDC electrolyte.
8. A method for preparing a composite cathode of an intermediate-temperature solid oxide fuel cell according to claim 2, wherein the calcining temperature in the step 5) is 900 ℃ and the time is 2 h.
9. A method for preparing a composite cathode of an intermediate-temperature solid oxide fuel cell according to claim 2, wherein the coating in the step 5) is performed by screen printing.
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Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08130018A (en) * | 1994-10-31 | 1996-05-21 | Nissan Motor Co Ltd | Electrode material for solid electrolyte |
| CN1465429A (en) * | 2002-06-27 | 2004-01-07 | 中国科学院大连化学物理研究所 | Two-phase mixed conductor oxygen-breathable film |
| CN1731607A (en) * | 2005-08-19 | 2006-02-08 | 黑龙江大学 | Solid oxide fuel cell cathode material |
| CN101257120A (en) * | 2008-04-11 | 2008-09-03 | 郭道传 | Process for synthesizing biphase nanometer fuel battery cathode material |
| CN101585558A (en) * | 2008-05-20 | 2009-11-25 | 中国科学院宁波材料技术与工程研究所 | The preparation method of nano-powder of cathode of solid oxide fuel cell |
| CN102054991A (en) * | 2010-11-23 | 2011-05-11 | 北京科技大学 | Cathode material of solid oxide fuel cell and preparation method thereof |
| CN102074277A (en) * | 2010-11-26 | 2011-05-25 | 中国科学院宁波材料技术与工程研究所 | Electrode material and electrode paste of oxygen sensor as well as preparation method of electrode |
| US20110143265A1 (en) * | 2009-12-10 | 2011-06-16 | Jain Kailash C | Low-Resistance Ceramic Electrode for a Solid Oxide Fuel Cell |
| CN102104153A (en) * | 2011-01-07 | 2011-06-22 | 上海交通大学 | Preparation method of cathode of low-medium temperature solid oxide fuel cell |
| KR20130097962A (en) * | 2012-02-27 | 2013-09-04 | 한국생산기술연구원 | Manufacturing method of cathode powder for solid oxide fuel cell using sol-gel process |
| CN103811788A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Preparation method for middle-temperature and low-temperature solid oxide fuel battery |
| CN104916850A (en) * | 2015-04-27 | 2015-09-16 | 上海邦民新能源科技有限公司 | Solid oxide fuel cell cathode material and solid oxide fuel cell composite cathode material and preparation method thereof and cell composite cathode preparation method |
| CN105399146A (en) * | 2015-08-17 | 2016-03-16 | 天津包钢稀土研究院有限责任公司 | Method for preparing La1-xSrxFe1-yCoyO3-[delta] powder through ammonium bicarbonate precipiation |
| JP2016059860A (en) * | 2014-09-17 | 2016-04-25 | トヨタ自動車株式会社 | Method for manufacturing fibrous perovskite type oxide catalyst |
| CN105789636A (en) * | 2016-03-22 | 2016-07-20 | 山西师范大学 | Method for one-step hydrothermal synthesis preparation of composite anode material of solid oxide fuel cell |
| CN106167276A (en) * | 2016-07-06 | 2016-11-30 | 南昌航空大学 | A kind of preparation method of laminated perovskite type nano material |
| CN106887604A (en) * | 2015-12-12 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of cathode material for solid-oxide fuel cell |
| CN108054393A (en) * | 2017-12-25 | 2018-05-18 | 河南工业大学 | A kind of preparation method of the intermediate temperature solid oxide fuel cell cathode with novel nano structure |
-
2020
- 2020-12-24 CN CN202011548580.XA patent/CN112687886B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08130018A (en) * | 1994-10-31 | 1996-05-21 | Nissan Motor Co Ltd | Electrode material for solid electrolyte |
| CN1465429A (en) * | 2002-06-27 | 2004-01-07 | 中国科学院大连化学物理研究所 | Two-phase mixed conductor oxygen-breathable film |
| CN1731607A (en) * | 2005-08-19 | 2006-02-08 | 黑龙江大学 | Solid oxide fuel cell cathode material |
| CN101257120A (en) * | 2008-04-11 | 2008-09-03 | 郭道传 | Process for synthesizing biphase nanometer fuel battery cathode material |
| CN101585558A (en) * | 2008-05-20 | 2009-11-25 | 中国科学院宁波材料技术与工程研究所 | The preparation method of nano-powder of cathode of solid oxide fuel cell |
| US20110143265A1 (en) * | 2009-12-10 | 2011-06-16 | Jain Kailash C | Low-Resistance Ceramic Electrode for a Solid Oxide Fuel Cell |
| CN102054991A (en) * | 2010-11-23 | 2011-05-11 | 北京科技大学 | Cathode material of solid oxide fuel cell and preparation method thereof |
| CN102074277A (en) * | 2010-11-26 | 2011-05-25 | 中国科学院宁波材料技术与工程研究所 | Electrode material and electrode paste of oxygen sensor as well as preparation method of electrode |
| CN102104153A (en) * | 2011-01-07 | 2011-06-22 | 上海交通大学 | Preparation method of cathode of low-medium temperature solid oxide fuel cell |
| KR20130097962A (en) * | 2012-02-27 | 2013-09-04 | 한국생산기술연구원 | Manufacturing method of cathode powder for solid oxide fuel cell using sol-gel process |
| CN103811788A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Preparation method for middle-temperature and low-temperature solid oxide fuel battery |
| JP2016059860A (en) * | 2014-09-17 | 2016-04-25 | トヨタ自動車株式会社 | Method for manufacturing fibrous perovskite type oxide catalyst |
| CN104916850A (en) * | 2015-04-27 | 2015-09-16 | 上海邦民新能源科技有限公司 | Solid oxide fuel cell cathode material and solid oxide fuel cell composite cathode material and preparation method thereof and cell composite cathode preparation method |
| CN105399146A (en) * | 2015-08-17 | 2016-03-16 | 天津包钢稀土研究院有限责任公司 | Method for preparing La1-xSrxFe1-yCoyO3-[delta] powder through ammonium bicarbonate precipiation |
| CN106887604A (en) * | 2015-12-12 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of cathode material for solid-oxide fuel cell |
| CN105789636A (en) * | 2016-03-22 | 2016-07-20 | 山西师范大学 | Method for one-step hydrothermal synthesis preparation of composite anode material of solid oxide fuel cell |
| CN106167276A (en) * | 2016-07-06 | 2016-11-30 | 南昌航空大学 | A kind of preparation method of laminated perovskite type nano material |
| CN108054393A (en) * | 2017-12-25 | 2018-05-18 | 河南工业大学 | A kind of preparation method of the intermediate temperature solid oxide fuel cell cathode with novel nano structure |
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