CN115241471A - Solid oxide fuel cell cathode material and preparation method and application thereof - Google Patents
Solid oxide fuel cell cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a solid oxide fuel cell cathode material with the chemical formula of Sr 4 Fe x Co y O 13+δ Wherein 0 is<x<4，2<y<6, δ is the oxygen vacancy concentration, 0<δ<1. The invention also discloses a preparation method of the cathode material of the solid oxide fuel cell, which comprises the following steps: weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water; sequentially dissolving in deionized water, heating and stirring to obtain gel; drying to obtain a precursor; carrying out decarbonization treatment on the precursor, and then carrying out oxygen partial pressure calcination to obtain powder; grinding the powder to obtain Sr 4 Fe x Co y O 13+δ A cathode material powder. The invention also discloses the oxygen ion conductor base at low temperatureSolid oxide fuel cells and low-temperature proton ceramic fuel cells. The solid oxide fuel cell cathode material prepared by the invention has excellent cell output performance.
Description
Technical Field
The invention belongs to a cathode material and a preparation method and application thereof, and particularly relates to a solid oxide fuel cell cathode material and a preparation method and application thereof.
Background
The Solid Oxide Fuel Cell (SOFC) is outstanding in developing clean energy due to the characteristics of high efficiency, no pollution, environmental friendliness and the like, is considered to be one of the most potential energy conversion devices, and has important significance in relieving energy crisis, environmental pollution and the like. Although SOFCs exhibit desirable electrochemical performance at higher operating temperatures, excessive temperatures also introduce problems such as excessive sealing costs, sintering of electrode materials, and thermal expansion mismatch that affect cell life. It is therefore a trend in SOFC development to lower the operating temperature.
With the decrease of the operating temperature, especially at the operating temperature below 600 ℃, the polarization resistance of the cathode material is sharply increased, the catalytic activity is significantly decreased, and the output power of the SOFC is affected, thereby limiting the practical application of the SOFC, so that it has been a research hotspot to develop a cathode material of a solid oxide fuel cell having high oxygen reduction activity and long-term stability at the operating temperature below 600 ℃.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to overcome the defects in the prior art, provides a solid oxide fuel cell cathode material which is efficient and stable for a long time, further aims to provide a simple, efficient and low-cost preparation method of the solid oxide fuel cell cathode material, further aims to provide an application of the solid oxide fuel cell cathode material in a low-temperature oxygen ion conductor-based solid oxide fuel cell, and further aims to provide an application of the solid oxide fuel cell cathode material in a low-temperature proton ceramic fuel cell.
The technical scheme is as follows: the cathode material of the solid oxide fuel cell has the chemical formula of Sr 4 Fe x Co y O 13+δ (SFC 4) of 0<x<4，2<y<6, δ is the oxygen vacancy concentration, 0<δ<1。
Further, the cathode material has an average particle diameter of 300 to 500nm.
The preparation method of the cathode material of the solid oxide fuel cell comprises the following steps:
step one, weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water according to a stoichiometric ratio;
step two, dissolving the raw materials in deionized water in sequence, and heating and stirring the mixture until the mixture is gelatinous;
step three, placing the product obtained in the step two in an oven for drying to obtain a precursor;
placing the precursor obtained in the step three in a muffle furnace for decarbonization treatment, and then performing oxygen partial pressure calcination to obtain powder;
step five, grinding the powder obtained in the step four to obtain Sr 4 Fe x Co y O 13+δ A cathode material powder.
Further, in the first step, ethylene diamine tetraacetic acid: citric acid monohydrate: the molar ratio of metal cations is 1.
Further, in the second step, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, heated and stirred to obtain a metal nitrate solution, ethylenediaminetetraacetic acid is dissolved in ammonia water, the ammonia water in which ethylenediaminetetraacetic acid is dissolved and citric acid monohydrate are added in the metal nitrate solution, and the mixture is continuously heated and stirred to be in a gel state. The heating temperature is 80-100 ℃, and the stirring speed is 200-300 r.min -1 . Heating to a temperature below 80 ℃ will retard the rate of gel formation; heating temperatures above 100 ℃ can result in shorter stirring times and gels tend to foam at high temperatures. The stirring speed is lower than 200 r.min -1 The complexing uniformity of metal ions is affected; the stirring speed is higher than 300 r.min -1 Resulting in splashing of the solution.
Furthermore, in the third step, the drying temperature is 200-300 ℃, and the drying time is 200-300 min. The drying temperature is lower than 200 ℃, which can cause insufficient carbonization of organic matters in the gel; the drying temperature is higher than 300 ℃, which can cause the carbon skeleton to burn.
Further, in the fifth step, the mixture is sieved by a 200-400-mesh sieve after being ground.
The application of the cathode material of the solid oxide fuel cell in the low-temperature oxygen ion conductor-based solid oxide fuel cell is disclosed, and Sr is used 4 Fe x Co y O 13+δ As a cathode, samarium oxide doped cerium oxide was used as an electrolyte, and a mixture of NiO and SDC was used as an anode.
The application of the cathode material of the solid oxide fuel cell in the low-temperature proton ceramic fuel cell is represented by Sr 4 Fe x Co y O 13+δ As a cathode, baZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ As the electrolyte, a mixture of NiO and bzcyb was used as the anode.
The preparation principle is as follows: sr 4 Fe x Co y O 13+δ The material is prepared from nano-scale monocalcium titanium ore phase Sr (Co, fe) O 3 Spinel phase (Co, fe) 3 O 4 Cobalt oxide CoO and strontium carbonate SrCO 3 And (4) forming. The catalyst comprises a monocalcite phase, a spinel phase and self-assembled mixture of strontium carbonate and cobalt oxide, wherein the monocalcite phase has excellent conductivity and better oxygen reduction activity, the spinel phase has lower conductivity but high oxygen reduction catalytic activity, and the existence of the strontium carbonate and the cobalt oxide reduces the thermal expansion coefficient and ensures long-time operation stability. Through the self-assembly mixing of the nano-scale catalyst of the system and the influence of synergistic effect, the battery prepared by the material is promoted to have excellent output power and long-term stability, has stable structure in a low-temperature range, and can show good ORR catalytic activity when applied to O-SOFC and PCFC.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. the prepared cathode material of the solid oxide fuel cell has excellent performanceThe output power of the prepared low-temperature proton ceramic fuel cell reaches 645mW cm at 550 DEG C -2 The output power of the prepared oxygen ion conductor-based fuel cell reaches 1250mW cm at 600 DEG C -2 ；
2. The prepared cathode material of the solid oxide fuel cell has excellent long-time thermochemical stability, the proton-based symmetric cell and the proton ceramic fuel cell can respectively continuously work for 1000h and 3100h at 550 ℃, the impedance and the output power of the proton-based symmetric cell are not obviously attenuated, the prepared oxygen ion-based symmetric cell can continuously work for 1000h at 550 ℃, the impedance of the oxygen ion-based symmetric cell is not obviously attenuated, and the thermal stability is good;
3. the prepared cathode material has wide application range and certain proton conductivity, so the material can be used as an O-SOFC cathode and is also suitable for PCFC;
4. the cathode material is synthesized by a simple sol-gel one-step method, the preparation method is simple and efficient, the cost of the raw material is low, and the method is suitable for industrial large-scale production;
5. the average particle size of the cathode material SFC4 is on the nanometer scale, so that the effective three-phase line length in the structure is increased, and the electrochemical reaction range is wider;
6. the method adopts oxygen partial pressure calcination, namely, in a closed environment, oxygen is gradually reduced along with calcination, so that carbonate can be generated, and the cathode material can stably work for a long time;
7. when the cathode material SFC4 is prepared, a layered perovskite phase is generated, and the structure has good chemical flexibility, higher conductivity and strong structural stability, so that the cathode material can stably work for a long time.
Drawings
FIG. 1 is an XRD pattern of an SFC4 cathode material of the invention;
fig. 2 is an impedance diagram of an oxygen ion based symmetric cell SFC4| SDC | SFC4 of the present invention at 550 ℃;
fig. 3 is a graph of the long term stability of an oxygen ion based symmetric cell SFC4| SDC | SFC4 of the present invention at 550 ℃;
FIG. 4 is a graph of the power output performance of an oxygen ion-based fuel cell SFC4| SDC | NiO-SDC of the present invention at temperatures of 400 ℃, 500 ℃ and 600 ℃;
FIG. 5 is an SEM image of a cross-section of an oxygen ion-based fuel cell SFC4| SDC | NiO-SDC of the present invention;
FIG. 6 is an impedance diagram of a proton-based symmetrical cell SFC4| BZCYb | SFC4 of the present invention at 550 ℃;
FIG. 7 is a graph of the long term stability of a proton-based symmetrical cell SFC4| BZCYb | SFC4 of the present invention at 550 ℃;
FIG. 8 is a graph of the power output performance of a proton ceramic fuel cell SFC4| BZCYb | NiO-BZCYb of the present invention at temperatures of 350 deg.C, 450 deg.C and 550 deg.C;
FIG. 9 is a SEM image of the cross section of a proton ceramic fuel cell SFC4| BZCYb | NiO-BZCYb of the present invention;
FIG. 10 is a graph of the long term stability of a proton ceramic fuel cell SFC4| BZCYb | NiO-BZCYb of the present invention at 550 ℃.
Detailed Description
In each of the following examples, the decarbonization treatment consisted in placing the precursor in a muffle furnace and calcining it at 700 ℃ for 5 hours. The mole number of the metal cations is the sum of the mole numbers of strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate.
Example 1
A preparation method of a solid oxide fuel cell cathode material comprises the following steps:
a. according to the stoichiometric ratio, strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water are respectively weighed, wherein the weight ratio of the ethylenediamine tetraacetic acid is as follows: citric acid monohydrate: the molar ratio of metal cations is 1;
b. firstly, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water at the temperature of 80 ℃ and the temperature of 300 r.min -1 Heating and stirring at the rotating speed of the temperature sensor to obtain a metal nitrate solution, simultaneously adding deionized water and ammonia water into the ethylenediaminetetraacetic acid, adding the ammonia water dissolved with the ethylenediaminetetraacetic acid and citric acid monohydrate into the metal nitrate solution, and continuing to heat at the temperature of 80 ℃ and at the temperature of 300 r.min -1 Is heated and stirred at the rotating speed ofUntil the solution becomes gel-like;
c. putting the gel obtained in the step b into a drying oven at 200 ℃ for drying for 300min to obtain a precursor;
d. placing the precursor obtained in the step c in a muffle furnace for decarbonization treatment, and then performing oxygen partial pressure calcination to obtain powder;
e. grinding the powder obtained in the fourth step, and sieving the powder by using a 200-mesh sieve to obtain Sr 4 Fe 0.5 Co 5.5 O 13+δ (SFC 4) cathode material powder having an average particle size of 300nm.
Example 2
A preparation method of a solid oxide fuel cell cathode material comprises the following steps:
a. according to the stoichiometric ratio, strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water are respectively weighed, wherein the weight ratio of the ethylenediamine tetraacetic acid is as follows: citric acid monohydrate: the molar ratio of metal cations is 1;
b. firstly, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water at the temperature of 100 ℃ and the temperature of 200 r.min -1 Heating and stirring at the rotating speed of (2) to obtain a metal nitrate solution, adding deionized water and ammonia water into ethylenediamine tetraacetic acid, adding the ammonia water dissolved with the ethylenediamine tetraacetic acid and citric acid monohydrate into the metal nitrate solution, and continuing to heat at the temperature of 100 ℃ and at the temperature of 200 r.min -1 Heating and stirring at the rotating speed of (1) until the solution becomes gel;
c. putting the gel obtained in the step b into a drying oven at 300 ℃ for drying for 200min to obtain a precursor;
d. placing the precursor obtained in the step c in a muffle furnace for decarbonization treatment, and then performing oxygen partial pressure calcination to obtain powder;
e. grinding the powder obtained in the fourth step, and sieving the powder by using a 400-mesh sieve to obtain Sr 4 Fe 3.5 Co 2.5 O 13+δ (SFC 4) cathode material powder having an average particle diameter of 500nm.
Example 3
A preparation method of a solid oxide fuel cell cathode material comprises the following steps:
a. according to the stoichiometric ratio, strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water are respectively weighed, wherein the weight ratio of the ethylenediamine tetraacetic acid is as follows: citric acid monohydrate: the molar ratio of metal cations is 1;
b. firstly, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water at the temperature of 95 ℃ and the temperature of 230 r.min -1 Heating and stirring at the rotating speed of the temperature-controlled device to obtain a metal nitrate solution, simultaneously adding deionized water and ammonia water into the ethylenediaminetetraacetic acid, adding the ammonia water dissolved with the ethylenediaminetetraacetic acid and citric acid monohydrate into the metal nitrate solution, and continuously heating at the temperature of 95 ℃ and the temperature of 230 r.min -1 Heating and stirring at the rotating speed of (1) until the solution becomes gel;
c. b, drying the gel obtained in the step b in an oven at 220 ℃ for 230min to obtain a precursor;
d. placing the precursor obtained in the step c in a muffle furnace for decarbonization treatment, and then performing oxygen partial pressure calcination to obtain powder;
e. grinding the powder obtained in the fourth step, and sieving the powder by using a 300-mesh sieve to obtain Sr 4 Fe 3 Co 5 O 13+δ (SFC 4) cathode material powder having an average particle diameter of 350nm.
Example 4
A preparation method of a solid oxide fuel cell cathode material comprises the following steps:
a. according to the stoichiometric ratio, strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water are respectively weighed, wherein the weight ratio of the ethylenediamine tetraacetic acid is as follows: citric acid monohydrate: the molar ratio of metal cations is 1;
b. firstly, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water at the temperature of 90 ℃ and the temperature of 300 r.min -1 Heating and stirring at the rotating speed of the solution to obtain a metal nitrate solution, simultaneously adding deionized water and ammonia water into the ethylenediamine tetraacetic acid, adding the ammonia water dissolved with the ethylenediamine tetraacetic acid and citric acid monohydrate into the metal nitrate solution, and continuing to perform stirring at 90 DEG CTemperature and 300 r.min -1 Heating and stirring at the rotating speed of (1) until the solution becomes gel;
c. putting the gel obtained in the step b into a drying oven at 250 ℃ for drying for 250min to obtain a precursor;
d. placing the precursor obtained in the step c in a muffle furnace for decarbonization treatment, and then performing oxygen partial pressure calcination to obtain powder;
e. grinding the powder obtained in the fourth step, and sieving the powder by using a 300-mesh sieve to obtain Sr 4 Fe 3 Co 4 O 13+δ (SFC 4) cathode material powder having an average particle diameter of 400nm.
The SFC4 cathode material synthesized in this example was characterized by X-ray diffraction (XRD) and the results are shown in fig. 1. From the results shown in FIG. 1, it is understood that the SFC4 cathode material is composed of nano-scale monocalcite phase Sr (Co, fe) O 3 Spinel phase (Co, fe) 3 O 4 Cobalt oxide CoO and strontium carbonate SrCO 3 And (4) forming. The Pmcn phase in fig. 1 is a space group of strontium carbonate, occupying 4.1% of the material. The carbonate can improve the oxygen activation performance and stability of the electrode material, which is one of the important reasons that a single cell prepared from the material can have higher output performance and long-term stability performance. In addition, the monocalcium phase has good conductivity, and the layered perovskite phase has high conductivity and long-term performance stability, which is the fundamental reason that a monocell prepared from the material can have high output performance and long-term stability.
Comparative example 1
The remaining steps of this comparative example are the same as example 4, except that: the temperature in step b was replaced by 70 ℃. As a result, it was found that: the gel formation rate decreases substantially.
Comparative example 2
The remaining steps of this comparative example are the same as example 4, except that: the temperature in step b was replaced with 110 ℃. As a result, it was found that: the stirring time is shortened, and the gel is easy to foam at high temperature.
Comparative example 3
The remaining steps of this comparative example are the same as example 4, except that: the temperature of the oven in step c was replaced by 180 ℃. As a result, it was found that: the organic matter in the gel is not carbonized enough.
Comparative example 4
The remaining steps of this comparative example are the same as example 4, except that: the temperature of the oven in step c was replaced with 320 ℃. As a result, it was found that: the carbon skeleton is excessively burned.
Example 5
SFC4| SDC | SFC4 oxygen ion-based symmetric cells were prepared using the SFC4 cathode material of example 4 by the following steps:
(1) Weighing 10ml of isopropanol, 2ml of ethylene glycol and 0.6ml of glycerol, weighing 1g of SFC4 cathode powder, and placing the powder on a planetary ball mill for ball milling, wherein the rotating speed of the ball mill is 400r min -1 Ball milling time is 2h, and cathode powder slurry is prepared;
(2) 0.5g of SDC electrolyte powder is weighed, pressed into a 15mm wafer by a tablet press and calcined for 5 hours in a high-temperature furnace at the temperature of about 1400 ℃, so as to prepare the electrolyte sheet.
(3) Uniformly spraying the slurry on two sides of an electrolyte sheet by using a spray gun, and calcining the electrolyte sheet in a muffle furnace at the temperature of about 800 ℃ for 2 hours to obtain a symmetrical battery;
(4) And brushing a current collecting layer on two sides of the oxygen ion-based symmetric battery, and connecting silver wires.
The SFC4| SDC | SFC4 oxygen ion-based symmetric cell prepared in this example was subjected to electrochemical impedance test in an air atmosphere at 550 ℃, and the results are shown in fig. 2. As can be seen from the results in FIG. 2, the resistance value of the SFC4| SDC | SFC4 oxygen ion-based symmetric cell was 0.04 Ω cm at the test temperature of 550 deg.C 2 。
The thermo-chemical stability of the SFC4| SDC | SFC4 oxygen ion-based symmetric cell prepared in this example was tested, and the results are shown in fig. 3. From the results in fig. 3, it can be seen that the oxygen ion-based symmetric cell prepared from the SFC4 cathode material can be operated for 1000 hours at the test temperature of 550 ℃, without a significant increase in impedance.
Example 6
An SFC4| SDC | NiO-SDC oxygen ion based fuel cell was prepared using the SFC4 cathode material of example 4, with the following specific steps:
(1) 10ml of isopropanol, 2ml of ethylene glycol and 0.6ml of glycerol are measured, 1g of SFC4 cathode powder is weighed and placed on a planetary ball mill for ball milling, and the rotating speed of the ball mill is 400r min -1 Ball milling time is 2h, and cathode powder slurry is prepared;
(2) Weighing 7g of NiO powder, 3g of SDC powder and 0.7g of PVB, placing the NiO powder, the SDC powder and the PVB in a mortar, pouring a proper amount of alcohol, grinding until the alcohol is completely volatilized, then placing the mixture in an oven to dry, and then placing the mixture in the mortar to grind the mixture into NiO-SDC anode powder.
(3) Weighing 0.35g of NiO-SDC anode powder, pressing the NiO-SDC anode powder into a 15mm wafer by using a tablet press, then weighing 0.015g of SDC electrolyte powder, uniformly sieving the SDC electrolyte powder onto one side surface of the anode powder wafer by using a 300-mesh sieve, continuously pressing, and calcining the pressed wafer in a high-temperature furnace at 1400 ℃ for 5 hours to prepare the half-cell wafer.
(4) Uniformly spraying the cathode powder slurry on one side of an electrolyte of a half cell by using a spray gun, and calcining for 2 hours in a muffle furnace at 800 ℃ to prepare an oxygen ion-based fuel cell;
(5) And brushing a current collecting layer on the cathode side of the oxygen ion-based fuel cell, connecting silver wires on two sides of the current collecting layer, and packaging the current collecting layer on a quartz glass tube.
The specific method for testing the output performance of the oxygen ion-based fuel cell prepared in the embodiment is as follows: in dry H 2 As a fuel, air was used as an oxidant and tested using a digital source meter (Keithley 2440) at temperatures of 400 deg.C, 500 deg.C and 600 deg.C, respectively, at a temperature interval of 50 deg.C, and the results are shown in FIG. 4, where the maximum power density at 600 deg.C was up to 1250mW cm -2 。
Figure 5 shows an SEM image of an oxygen ion-based fuel cell prepared in this example, comprising the cross-sectional image shapes of an SFC4 porous cathode, a dense SDC electrolyte and a NiO-SDC composite anode. As can be seen in fig. 5, the adhesion between the SFC4 cathode (thickness of about 25 μm) and the SDC electrolyte (thickness of about 20 μm) is very tight, thus demonstrating the reliability of the performance test results for the oxygen ion-based fuel cell.
Example 7
The SFC4| BZCYYb | SFC4 proton-based symmetric cell was prepared using the SFC4 cathode material of example 4, with the following specific steps:
(1) 10ml of isopropanol, 2ml of ethylene glycol and 0.6ml of glycerol are measured, 1g of SFC4 cathode powder is weighed and placed on a planetary ball mill for ball milling, and the rotating speed of the ball mill is 400r min -1 Ball milling time is 2h, and cathode powder slurry is prepared;
(2) About 0.5g of BZCYb electrolyte powder is weighed, pressed into a wafer with the diameter of 15mm by a tablet machine and calcined for 5 hours in a high-temperature furnace at about 1450 ℃, so that the electrolyte sheet is prepared.
(3) Uniformly spraying the slurry on two sides of an electrolyte sheet by using a spray gun, and calcining the electrolyte sheet in a muffle furnace at the temperature of about 800 ℃ for 2 hours to obtain a symmetrical battery;
(4) And brushing a current collecting layer on two sides of the proton-based symmetrical battery, and connecting silver wires.
Wet air (3% H) at 550 ℃ for SFC 4. Sub.BZCYb. Sub.SFC 4 proton-based symmetrical Battery prepared in this example 2 O) was performed in an atmosphere, and the results are shown in fig. 6. From the results in fig. 6, it can be seen that the resistance of the symmetric cell made of SFC4 cathode material is 0.774 Ω cm at 550 ℃ 2 。
The thermo-chemical stability of the SFC4| bzcyb | SFC4 proton-based symmetric battery prepared in this example was tested, and the results are shown in fig. 7. As can be seen from the results shown in FIG. 7, the SFC4| BZCYb | SFC4 proton-based symmetrical battery can continuously operate for 1000 hours at a test temperature of 550 ℃, and the impedance thereof is 4/10000 Ω cm 2 The rate of/h is increasing.
Example 8
The preparation method of the SFC4| bzcyy | SFC4 proton ceramic fuel cell in this embodiment includes the following specific steps:
(1) 10ml of isopropanol, 2ml of ethylene glycol and 0.6ml of glycerol are measured, 1g of SFC4 cathode powder is weighed and placed on a planetary ball mill for ball milling, and the rotating speed of the ball mill is 400r min -1 Ball milling time is 2h, and cathode powder slurry is prepared;
(2) Weighing 6g of NiO powder, 4g of BZCYb powder and 1g of starch, placing the powder and the starch in a ball milling tank, and pouring a proper amount of alcoholPlacing on a planetary ball mill for 400r min -1 Ball-milling at a rotating speed of 40min, pouring the ball-milled slurry into a mortar, grinding until all alcohol is volatilized, then placing the mixture into an oven for drying, and then placing the mixture into the mortar for grinding into NiO-BZCYb anode powder.
(3) Weighing 0.35g of NiO-BZCYb anode powder, pressing the NiO-BZCYb anode powder into a wafer of 15mm by using a tablet press, weighing 0.015g of BZCYb electrolyte powder, uniformly sieving the BZCYb electrolyte powder onto the surface of one side of the anode powder wafer by using a 300-mesh sieve, continuing pressing, and calcining the pressed wafer in a high-temperature furnace at 1450 ℃ for 10 hours to obtain the half-cell wafer.
(4) Uniformly spraying the cathode powder slurry on one side of an electrolyte of a half cell by using a spray gun, and calcining for 2 hours in a muffle furnace at 800 ℃ to prepare a proton ceramic fuel cell;
(5) And brushing a current collecting layer on the cathode side of the single cell, connecting silver wires on two sides of the current collecting layer, and packaging the current collecting layer on a quartz glass tube.
The specific method for testing the output performance of the proton ceramic fuel cell prepared in the embodiment is as follows: by wetting H 2 (3％H 2 O) as fuel, and air as oxidant at 350 deg.C, 450 deg.C and 550 deg.C respectively, and using digital source meter (Keithley 2440), the results are shown in FIG. 8, and the maximum power density at 550 deg.C can reach 645mW cm -2 。
Fig. 9 shows an SEM image of a proton ceramic fuel cell prepared in this example, comprising the cross-sectional image shapes of an SFC4 porous cathode, a dense bzcyb electrolyte and a NiO-bzcyb composite anode. It is evident from the figure that the adhesion between the SFC4 cathode (thickness of about 30 μm) and the bzcyb electrolyte (thickness of about 25 μm) is still very tight, which also demonstrates the reliability of the performance test results for the proton ceramic fuel cell.
The thermochemical stability test of the proton ceramic fuel cell prepared in this example was carried out by the following specific methods: in dry H 2 For fuel, stability testing was performed using a digital source meter (Keithley 2440) using air as the oxidant at a temperature of 550 ℃, and the results are shown in fig. 10, which allowed continuous stable operation 3100h at a test temperature of 550 ℃.
Claims (10)
1. A solid oxide fuel cell cathode material, characterized by: has a chemical formula of Sr 4 Fe x Co y O 13+δ Wherein 0 is<x<4，2<y<6, δ is the oxygen vacancy concentration, 0<δ<1。
2. The solid oxide fuel cell cathode material of claim 1, wherein: the average grain diameter of the cathode material is 300-500 nm.
3. The method for preparing the cathode material of the solid oxide fuel cell according to any one of claims 1 to 2, comprising the steps of:
step one, weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediamine tetraacetic acid, citric acid monohydrate and ammonia water according to a stoichiometric ratio;
step two, dissolving the raw materials in deionized water in sequence, and heating and stirring the mixture until the mixture is gelatinous;
step three, drying the product obtained in the step two to obtain a precursor;
step four, performing decarbonization treatment on the precursor obtained in the step three, and then performing oxygen partial pressure calcination to obtain powder;
step five, grinding the powder obtained in the step four to obtain Sr 4 Fe x Co y O 13+δ A cathode material powder.
4. The method for preparing a cathode material of a solid oxide fuel cell according to claim 3, wherein: in the first step, ethylene diamine tetraacetic acid: citric acid monohydrate: the molar ratio of metal cations is 1.
5. The method for preparing a cathode material of a solid oxide fuel cell according to claim 3, wherein: in the second step, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, heated and stirred to obtain a metal nitrate solution, ethylenediaminetetraacetic acid is dissolved in ammonia water, the ammonia water in which the ethylenediaminetetraacetic acid is dissolved and citric acid monohydrate are added into the metal nitrate solution, and the mixture is continuously heated and stirred to be in a gel state.
6. The method for preparing a cathode material of a solid oxide fuel cell according to claim 3, wherein: in the second step, the heating temperature is 80-100 ℃, and the stirring speed is 200-300 r.min -1 。
7. The method for preparing a cathode material of a solid oxide fuel cell according to claim 3, wherein: in the third step, the drying temperature is 200-300 ℃, and the time is 200-300 min.
8. The method for preparing a cathode material of a solid oxide fuel cell according to claim 3, wherein: in the fifth step, the mixture is sieved by a 200-400 mesh sieve after being ground.
9. The use of the cathode material of the solid oxide fuel cell according to any one of claims 1 to 2 in a low temperature oxygen ion conductor based solid oxide fuel cell, wherein: by Sr 4 Fe x Co y O 13+δ And as a cathode, samarium oxide doped cerium oxide is used as an electrolyte, and a mixture of NiO and SDC is used as an anode.
10. The use of the solid oxide fuel cell cathode material of any one of claims 1-2 in a low temperature proton ceramic fuel cell, wherein: by Sr 4 Fe x Co y O 13+δ As cathode, baZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ As the electrolyte, a mixture of NiO and bzcyb was used as the anode.
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| CN202211016544.8A CN115241471A (en) | 2022-08-23 | 2022-08-23 | Solid oxide fuel cell cathode material and preparation method and application thereof |
| PCT/CN2022/127371 WO2024040735A1 (en) | 2022-08-23 | 2022-10-25 | Solid oxide fuel cell cathode material, and preparation method therefor and use thereof |
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| CN116864703A (en) * | 2023-09-04 | 2023-10-10 | 中石油深圳新能源研究院有限公司 | Fuel cell cathode material, preparation method thereof, fuel cell and cathode thereof |
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| CN109742414A (en) * | 2019-01-09 | 2019-05-10 | 渤海大学 | A kind of intermediate temperature solid oxide fuel cell cathode material and the preparation method and application thereof |
| CN112928314A (en) * | 2021-01-23 | 2021-06-08 | 西安石油大学 | Preparation method of solid oxide fuel cell |
| CN113839054B (en) * | 2021-04-02 | 2023-06-02 | 南京工业大学 | Reversible proton ceramic battery electrode material and preparation method and application thereof |
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| CN116864703A (en) * | 2023-09-04 | 2023-10-10 | 中石油深圳新能源研究院有限公司 | Fuel cell cathode material, preparation method thereof, fuel cell and cathode thereof |
| CN116864703B (en) * | 2023-09-04 | 2024-01-05 | 中石油深圳新能源研究院有限公司 | Fuel cell cathode material, preparation method thereof, fuel cell and cathode thereof |
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