CN112047381A - Cathode with crystal face preferentially exposed for solid oxide fuel cell and preparation method and application thereof - Google Patents

Cathode with crystal face preferentially exposed for solid oxide fuel cell and preparation method and application thereof Download PDF

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CN112047381A
CN112047381A CN201910487935.XA CN201910487935A CN112047381A CN 112047381 A CN112047381 A CN 112047381A CN 201910487935 A CN201910487935 A CN 201910487935A CN 112047381 A CN112047381 A CN 112047381A
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cathode
crystal face
oxide
fuel cell
spinel
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杨维慎
刘焕英
朱雪峰
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a preparation method of a crystal face preferential exposure cathode of a solid oxide fuel cell, which adopts a high-temperature electric roasting method of oxides with irregular shapes. The cathode is an oxide material and has a spinel structure; the preferential exposure of the crystal face of the oxide with the spinel structure is an octahedron, and the preparation method of the cathode with the preferential exposure of the crystal face is a high-temperature electric roasting method of the oxide with the irregular morphology to obtain the oxide with the preferential exposure of the crystal face; and finally, preparing the oxide with the preferentially exposed crystal face into a cathode blank by one or more methods of a screen printing method, a coating and scraping method, a tape casting method and a spin coating method, wherein the cathode blank is prepared on the electrolyte of the solid oxide fuel cell, and the corresponding single cell with the preferentially exposed crystal face is obtained by roasting at the temperature of 600-1300 ℃ for 0.1-50 hours. The crystal face preferentially exposes the cathode and has better electrocatalytic activity on oxygen reduction reaction.

Description

Cathode with crystal face preferentially exposed for solid oxide fuel cell and preparation method and application thereof
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to an oxide with a spinel structure and oriented with a preferred crystal face, a preparation method thereof and application thereof in a solid fuel cell cathode.
Background
A Solid Oxide Fuel Cell (SOFC) is a green energy conversion device that directly converts energy released from a chemical reaction of a substance into electrical energy. Generally, a fuel such as hydrogen, carbon, low-carbon alkane, or methanol is used as a negative electrode (anode), and oxygen in the air is used as a positive electrode (cathode). The battery has the advantages of high conversion efficiency, full ceramics, environmental friendliness, wide fuel application range, no need of charging and the like, and is expected to become an effective way for realizing energy source cleaning in the 21 st century. The oxygen reduction reaction of the SOFC cathode is composed of a plurality of elementary steps, including diffusion of oxygen in a viscous layer and a cathode pore channel, exchange reaction on the surface of the cathode, diffusion in a bulk phase, transmission at a cathode/electrolyte interface and the like, and the deep research on the reaction mechanism is very helpful for optimizing the cathode structure and improving the cathode electrocatalytic activity. The oxygen reduction reaction mechanism has great difference with the difference of cathode materials, structures, exposed crystal faces and working environments, and particularly, the reaction process is directly related to the chemical properties (element composition, atom arrangement structure, oxygen vacancy concentration and the like) of the surface of the cathode material. The orientation of crystal planes was found by professor Wuniang Jiang, university of West Virginia]La of (2)0.5Sr0.5MnO3-The micron cube is used as the SOFC cathode, the polarization resistance of the micron cube is obviously smaller than that of a randomly oriented cathode, and the functional relationship between the exchange current density and the oxygen partial pressure shows that the crystal plane orientation is 200]The step of controlling the speed of the above oxygen reduction reaction is charge transport with random orientationThe rate control step for the cathode is oxygen adsorption dissociation (Energy environ. sci.,2011,4(1), 139-144). Therefore, the crystal face orientation can directly influence the electrocatalytic activity of the cathode, the oxygen reduction reaction process and the kinetic parameters. In order to further promote the commercial development and large-scale application of the SOFC, the preparation of the cathode with the preferentially exposed crystal face is particularly important.
Disclosure of Invention
Based on the above background technology, the present invention aims to provide a method for preparing a cathode with a crystal plane preferentially exposed in a solid oxide fuel cell. The technical scheme is as follows:
the invention provides a preparation method of spinel oxide with a preferred crystal face, which adopts a high-temperature electric roasting method of spinel oxide with irregular morphology, and comprises the following steps: spinel oxide AxByOzPlacing the material in a calcining furnace, introducing a current of 1mA-10A, heating to 500-1300 ℃ in a certain calcining atmosphere, calcining for 1-300 h, and cooling to obtain the preferred crystal face spinel oxide; the calcining atmosphere is oxidizing atmosphere or inert atmosphere. The spinel oxide is commercially available, or a metal salt or oxide is used as a raw material according to a reference document, and one or more of a complex method, a coprecipitation method and a solid synthesis method are adopted to prepare the spinel oxide with a random morphology.
Based on the technical scheme, preferably, the particle size of the spinel oxide is 1nm-5 μm; the oxidizing atmosphere gas is air, oxygen or oxygen-inert gas mixture; the inert atmosphere gas and the inert gas are independently selected from helium, nitrogen or argon; the heating and cooling rates are 0.01 ℃/min to 100 ℃/min.
Based on the above technical solution, preferably, a is at least one of metal elements, B is at least one of metal elements, and at least one transition metal element of the fourth period is in a group of a and B, and preferably, neither a nor B is an alkaline earth metal, and the addition of an alkali metal may destroy the stability of the alkali metal structure; x ranges from 0 to 3; y ranges from 0 to 3, the sum of x and y is 3, and z is 4.
The invention also provides a preferred crystal face spinel oxide prepared by the preparation method, wherein the preferred crystal face spinel oxide is a regular octahedron exposing a [111] and/or [011] crystal face; the grain size of the preferred crystal face spinel is 1nm-5 mu m.
In yet another aspect, the present invention provides a solid oxide fuel cell cathode comprising the above preferred crystal plane spinel oxide.
The invention also provides a preparation method of the solid oxide fuel cell cathode, which comprises the following steps:
(1) coating the spinel oxide with the preferred crystal face on an electrolyte of a solid oxide fuel cell by a screen printing method, a coating and scraping method, a tape casting method and a spin coating method to prepare a cathode blank;
(2) and (2) calcining the cathode blank obtained in the step (1) at 600-1300 ℃ for 0.1-50 h to obtain the solid oxide fuel cell cathode, namely the cathode with crystal planes preferentially exposed.
Based on the technical scheme, preferably, the electrolyte is ZrO2Base electrolyte, CeO2A base electrolyte, or an LSGM base electrolyte or Ba (Ce, Zr) O3A base electrolyte.
The invention also provides an application of the solid oxide fuel cell cathode, wherein the working temperature range of the solid oxide fuel cell is 200-1000 ℃. The crystal plane preferential exposure cathode is stably existed in the working atmosphere of the solid oxide fuel cell, and the working atmosphere is oxidizing gas. The cathode is stable for 1-40000h in the working temperature range and the working atmosphere of the solid oxide fuel cell; the working temperature range is 200-1000 ℃; the working atmosphere is an oxidizing atmosphere.
Advantageous effects
(1) The preparation method of the solid oxide fuel cell crystal face preferred exposure cathode provided by the invention has the advantages that: the electrocatalytic activity of the crystal face preferential exposure cathode on the oxygen reduction reaction is good, and the crystal face preferential exposure effect and the oxygen reduction reaction mechanism are deeply understood, which is helpful for the development of SOFC cathodes in the future to provide a feasible solution.
(2) The spinel oxide does not contain alkaline earth metal elements, so that the structure of the spinel oxide is more stable, and particularly, the spinel oxide does not have crystal phase change when being used as a cathode.
(3) The preparation method is completed by high-temperature calcination under the action of an electric field, the electric field is favorable for surface atomic rearrangement of the spinel oxide, and the electric field promotes the exposure of a preferred crystal face of the spinel oxide; high temperature calcination is also beneficial to the surface atomic rearrangement of the spinel oxide, and the spinel oxide with preferentially exposed crystal planes obtained at high temperature is stable at high temperature, and the stability of the preferentially exposed crystal planes in subsequent cathode applications is important. The spinel oxide with the preferred exposed crystal face exposes a [111] (cubic spinel phase) or a [011] crystal face (tetragonal spinel phase), the spinel oxide with the preferred exposed crystal face contains at least one transition metal element, and the transition metal element has a variable oxidation state and is beneficial to electrocatalysis of an oxygen reduction reaction on a cathode side.
(4) The grain diameter of the preferred crystal face spinel prepared by the invention is 1nm-5 mu m, the grain is small, the specific surface is large, and the area of a cathode side triple point (active point of oxygen reduction reaction) is increased. The control of the grain size of the preferred crystal face spinel is influenced by two steps, the first step is the grain size of the precursor (i.e. the initial spinel oxide powder in the calcination process under the action of current), and the second step is the influence of the calcination process under the action of current on the grain size. Generally, the precursor is synthesized by a complex method, and the particle size is 1nm-5 μm. The grain size of the preferred crystal face spinel oxide obtained in the calcining process under the action of current is 1nm-5 mu m, namely the influence of the calcining process under the action of current on the grain size is small.
Drawings
FIG. 1 is a diagram of the components of an electric roasting apparatus of the present invention; wherein: 1. a metal mesh; 2. a metal wire; 3. a quartz tube I; 4. a quartz tube II; 5. and a quartz tube III.
Fig. 2 is a scanning electron micrograph of a crystal plane-preferentially-exposed cathode (spinel-structured oxide) prepared in example 1.
Fig. 3 is a high resolution transmission electron micrograph of a crystal plane preferentially exposed cathode (spinel structure oxide) prepared in example 1.
Fig. 4 is a scanning electron micrograph of a corresponding single cell having a crystal plane preferentially exposed cathode (spinel structure oxide) prepared in example 1.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The method comprises the following specific steps of preparing a crystal face preferential exposure cathode by adopting a high-temperature electric roasting method of an oxide with a random morphology:
preparing an oxide with a random morphology by taking metal salt or an oxide as a raw material and adopting one or more of a complex method, a coprecipitation method and a solid synthesis method; placing the obtained irregular shape oxide into a high-temperature furnace, heating at a certain speed, heating to a certain temperature for heat preservation, and then cooling at a certain speed to obtain an oxide with a crystal face preferentially exposed; in the high-temperature roasting process, electrifying the oxide with irregular appearance; in the high-temperature roasting process, introducing roasting gas; preparing the oxide with the crystal face preferentially exposed into a cathode blank by one or more methods of a screen printing method, a coating and scraping method, a tape casting method and a spin coating method, wherein the cathode blank is prepared on the electrolyte of the solid oxide fuel cell; and roasting the obtained crystal face preferential exposure cathode blank at a certain temperature to obtain the crystal face preferential exposure cathode. The particle size of the irregular morphology oxide is between 1nm and 5 μm. The oxide with irregular shape is put into a high temperature furnace, and the temperature rising and falling speed is between 0.01 ℃/min and 30 ℃/min. The temperature range of heat preservation is 500 ℃ to 1300 ℃, and the heat preservation time is 1 hour to 300 hours. The current for applying the power is between 1mA and 10A. The roasting gas is one or more of oxidizing gas (air, oxygen) and inert gas (argon, nitrogen and helium). The cathode blank is prepared on the electrolyte of the solid oxide fuel cell, and the electrolyte is ZrO2Base electrolyte or CeO2A base electrolyte or LSGM base electrolyte or Ba (Ce, Zr) O3A base electrolyte. The roasting temperature of the crystal face preferentially exposing the cathode blank is 600-1300 ℃, and the heat preservation time is 0.1-50 hours.
The invention realizes the electric roasting through a general tube furnace and an electric device, the sample powder is placed on a metal net, and the electric roasting is realized through the electrification of the metal net.
The electric roasting of the invention can be realized by the components shown in figure 1, a powder sample is placed on a metal net 1, the metal net 1 is fixed by a quartz tube I3 and a quartz tube II 4, two ends of the metal net are respectively connected with metal wires 2, the two metal wires 2 are pulled out of the quartz tube and are connected with an electric device, the power-up of the powder sample can be realized, the quartz tube I3 and the quartz tube II 4 which are fixed with the metal net 1 are integrally placed in a quartz tube III 5, and then the quartz tube III 5 is integrally placed in a tube furnace to realize the electric roasting. And the roasting gas is introduced from the gap between the quartz tube I3 and the quartz tube II 4 to reach the sample powder, and the treated gas enters the quartz tube III 5 and is discharged from the quartz tube III 5.
Example 1
According to the technical scheme of the invention, 0.01mol of Zn (NO) is added3)3·6H2O、0.09mol Co(NO3)3·6H2Dissolving O, 0.2mol of citric acid and 0.3mol of EDTA in deionized water, adding a proper amount of ammonia water, adjusting the pH value of the solution to 7-8, and magnetically stirring to form a uniform solution; the spinel oxide with the irregular morphology can be prepared by oxides with general structures or references (Chemical Communications 2011,47, 2378-. Then put into a high temperature furnace with 5 percent of O2Under the condition of-He atmosphere, the current of electricity is 10A, the temperature rising speed is 50 ℃/min, the temperature is kept at 500 ℃ for 290 hours, the temperature reducing speed is 50 ℃/min, the temperature is reduced to the room temperature, and the spinel oxide Zn with the crystal face preferentially exposed is obtained0.3Co2.7O4(see FIGS. 2 and 3), the particle size is about 2 μm, and the [111] is preferentially exposed]A crystal plane. Oxide Zn with the crystal face exposed preferentially0.3Co2.7O4Preparing cathode blank by spin coating, the cathode blank is ZrO of solid oxide fuel cell2Preparing on a base electrolyte, roasting at 1300 ℃, and keeping the temperature for 1 hour to obtain crystal face preferentially exposed cathode Zn0.3Co2.7O4The single cell (shown in FIG. 4) of (1) has a particle diameter of about 2 μm, and is preferentially exposed to [111]]A crystal plane.
Example 2
According to the technical scheme of the invention, Fe with a spinel structure is purchased3O4Powder (particle size about 200 nm). Then placing the alloy in a high-temperature furnace in nitrogen atmosphere, heating with the current of 5mA at the heating speed of 1 ℃/min, keeping the temperature at 1300 ℃ for 1 hour, and cooling to room temperature at the cooling speed of 2 ℃/min to obtain Fe with crystal face preferentially exposed3O4Particle size of about 200nm, preferentially exposed [011]]A crystal plane. The obtained oxide Fe with the crystal face preferentially exposed3O4Preparing a cathode blank by a screen printing method, wherein the cathode blank is prepared on an LSGM-based electrolyte of a solid oxide fuel cell, the roasting temperature is 800 ℃, the heat preservation time is 50 hours, and the flaky crystal face preferentially exposed cathode Fe is obtained3O4Preferentially expose [011]]A crystal plane.
Example 3
According to the technical scheme of the invention, 0.05mol of Mn (NO) is added3)2Aqueous solution, 0.05mol of Cu (CH)3COO)2·H2Dissolving O and 0.3mol of glycine into deionized water, adding a proper amount of ammonia water, adjusting the pH value of the solution to 7-8, and magnetically stirring to form a uniform solution; heating and stirring to form gel, and roasting to obtain spinel-structured oxide with irregular morphology and particle size of about 300 nm. Then placing the mixture in a high-temperature furnace in argon atmosphere, heating at the current of 1A at the heating speed of 10 ℃/min, keeping the temperature at 800 ℃ for 100 hours, and cooling to room temperature at the cooling speed of 100 ℃/min to obtain the spinel oxide Cu with preferentially exposed crystal faces1.5Mn1.5O4Particle size of about 300nm, preferentially exposed [011]]Crystal face and [111]]A crystal plane. Oxide Cu with the crystal face preferentially exposed1.5Mn1.5O4Preparing cathode blank by coating and scraping method, the cathode blank is CeO in solid oxide fuel cell2Preparing on a base electrolyte, roasting at 1000 ℃, and keeping the temperature for 20 hours to obtain crystal face preferentially exposed cathode Cu1.5Mn1.5O4Has a particle diameter of about 300nm, and preferentially exposes [011]]Crystal face and [111]]A crystal plane.
Example 4
According to the technical scheme of the invention, 0.09mol of Co (CH) is respectively added3COO)2·4H2O、0.0033mol Ni(NO3)3·6H2O、0.0033mol Bi(NO3)3·5H2O、0.0033mol AgNO30.3mol of glycine is dissolved in deionized water, a proper amount of ammonia water is added, the pH value of the solution is adjusted to 7-8, and the solution is magnetically stirred to form a uniform solution; heating and stirring to form gel, and roasting to obtain spinel-structured oxide with irregular morphology and particle size of about 500 nm. Then placing the mixture in a high-temperature furnace in oxygen atmosphere, heating the mixture at the current of 500mA at the heating speed of 5 ℃/min, keeping the temperature at 1000 ℃ for 150 hours, and cooling the mixture to room temperature at the cooling speed of 20 ℃/min to obtain spinel oxide Ni with preferentially exposed crystal faces0.1Bi0.1Ag0.1Co2.7O4Particle size of about 500nm, preferentially exposed [111]]A crystal plane. Oxide Ni with the crystal face exposed preferentially0.1Bi0.1Ag0.1Co2.7O4Preparing cathode blank by tape casting method, the cathode blank is Ba (Ce, Zr) O in solid oxide fuel cell3Preparing on a base electrolyte, roasting at 1100 ℃, and keeping the temperature for 10 hours to obtain crystal face preferentially exposed cathode Ni0.1Bi0.1Ag0.1Co2.7O4Has a particle diameter of about 500nm, and is preferentially exposed to [111]]A crystal plane.
Example 5
According to the technical scheme of the invention, 0.09mol of Mn (CH) is added3COO)2·4H2O、0.0033mol Sm(NO3)3·6H2O、0.0033mol KNO3、0.00047mol H24Mo7N6O24·4H2Dissolving O (ammonium molybdate tetrahydrate) and 0.3mol of glycine into deionized water, adding a proper amount of ammonia water, adjusting the pH value of the solution to 7-8, and magnetically stirring to form a uniform solution; heating and stirring to be gelatinous, and roasting to obtain the oxide with the irregular appearance and the spinel structure, wherein the grain diameter is about 800 nm. Then placing the mixture in a high-temperature furnace in oxygen atmosphere, applying electricity at a current of 5A and a temperature rise speed of 30 ℃/min, and keeping the temperature at 900 ℃ for 200 hoursCooling to room temperature at a cooling rate of 20 ℃/min to obtain spinel oxide Sm with preferentially exposed crystal faces0.1K0.1Mo0.1Co2.7O4Particle size of about 500nm, preferentially exposed [011]]A crystal plane. Oxide Sm with the crystal face exposed preferentially0.1K0.1Mo0.1Co2.7O4Preparing cathode blank by tape casting method, the cathode blank is Ba (Ce, Zr) O in solid oxide fuel cell3Preparing on a base electrolyte, roasting at 1100 ℃, and keeping the temperature for 10 hours to obtain a crystal face preferred exposure cathode Sm0.1K0.1Mo0.1Co2.7O4Has a particle diameter of about 800nm, and preferentially exposes [011]]A crystal plane.
Example 6
According to the technical scheme of the invention, 0.07mol of manganese sesquioxide, 0.03mol of cobaltosic oxide, ethanol and starch are respectively and uniformly mixed, put into a ball milling tank for ball milling, and then roasted to obtain the oxide with the irregular appearance and the spinel structure, wherein the particle size is about 5 mu m. Then placing the mixture in a high-temperature furnace in helium atmosphere, wherein the current of electrification is 500mA, the heating rate is 10 ℃/min, the temperature is kept for 299 hours at 500 ℃, the cooling rate is 10 ℃/min, and the temperature is reduced to room temperature to obtain spinel oxide Mn with preferentially exposed crystal faces2.1Co0.9O4Particle size of about 5 μm, preferentially exposed [011]]A crystal plane. Oxide Mn with the crystal face exposed preferentially2.1Co0.9O4Preparing cathode blank by coating and scraping method, the cathode blank is ZrO of solid oxide fuel cell2Preparing on a base electrolyte, roasting at 1300 ℃, and keeping the temperature for 0.2 h to obtain crystal face preferentially exposed cathode Mn2.1Co0.9O4Has a particle diameter of about 5 μm and is preferentially exposed to [011]]A crystal plane. The output performance of the single cell is tested, and the maximum output power densities of the single cell at 800 ℃, 750 ℃ and 700 ℃ are 2000 mW cm, 1600 mW cm and 1300mW cm respectively-2。
Example 7
According to the technical scheme of the invention, 0.09mol of Fe (NO) is respectively added3)3·6H2O、0.0033mol Mg(CH3COO)2、0.0033mol Y(NO3)3·6H2O、0.0033mol Zr(CH3COO)4Dissolving 0.2mol of citric acid and 0.3mol of EDTA in deionized water, adding a proper amount of ammonia water, adjusting the pH value of the solution to 7-8, and magnetically stirring to form a uniform solution; heating and stirring to form gel, and roasting to obtain irregular oxide with particle size of about 50 nm. Then placing the mixture in a high-temperature furnace in air atmosphere, heating at 2A with the heating rate of 20 ℃/min, keeping the temperature at 900 ℃ for 60 hours, cooling to room temperature at the cooling rate of 20 ℃/min to obtain spinel oxide Mg with crystal face preferentially exposed0.1Y0.1Zr0.1Fe2.7O4Particle size of about 80nm, preferentially exposed [011]]A crystal plane. Oxide Mg with preferentially exposed crystal face0.1Y0.1Zr0.1Fe2.7O4Preparing cathode blank by spin coating, the cathode blank is ZrO of solid oxide fuel cell2Preparing on a base electrolyte, roasting at 600 ℃, and keeping the temperature for 60 hours to obtain crystal face preferentially-exposed cathode Mg0.1Y0.1Zr0.1Fe2.7O4Has a particle diameter of about 100nm, and preferentially exposes [011]]A crystal plane.
Example 8
According to the technical scheme of the invention, 0.09mol of Mn (NO) is added3)2Aqueous solution, 0.0033mol of Na2WO4·2H2Dissolving O, 0.2mol of citric acid and 0.3mol of EDTA in deionized water, adding a proper amount of ammonia water, adjusting the pH value of the solution to 7-8, and magnetically stirring to form a uniform solution; heating and stirring to form gel, and roasting to obtain irregular oxide with particle size of about 200 nm. Then placed in a high temperature furnace with 10% O2-N2Mixing gas, heating with 200mA current at 40 deg.C/min, maintaining at 700 deg.C for 160 hr, cooling to room temperature at 2 deg.C/min to obtain spinel oxide Na with crystal face preferentially exposed0.2W0.1Mn2.7O4Particle size of about 200nm, preferentially exposed [011]]A crystal plane. Oxide Na with the crystal face exposed preferentially0.2W0.1Mn2.7O4Preparing cathode blank by coating and scraping method, wherein the cathode blank is prepared by coating solid oxygenCeO of compound fuel cell2Preparing on a base electrolyte, roasting at 1050 ℃, and keeping the temperature for 15 hours to obtain crystal face preferentially-exposed cathode Na0.2W0.1Mn2.7O4Has a particle diameter of about 200nm, and preferentially exposes [011]]A crystal plane.
Example 9
Synthesizing MnCo by citric acid-EDTA complexation method2O4Powder (particle size about 300nm, no preferentially exposed crystal planes). Then placing the mixture in a high-temperature furnace in nitrogen atmosphere, heating the mixture at the current of 500mA at the heating speed of 10 ℃/min, keeping the temperature at 800 ℃ for 100 hours, and cooling the mixture to room temperature at the cooling speed of 10 ℃/min to obtain the spinel oxide MnCo with crystal face preferentially exposed2O4Particle size of about 300nm, preferentially exposed [111]]A crystal plane. The obtained oxide MnCo with the crystal face preferentially exposed2O4Preparing cathode blank by coating and scraping method, wherein the cathode blank is 8% Y of solid oxide fuel cell2O3-ZrO2Roasting on the electrolyte at 1100 ℃ for 20 hours to obtain a crystal face preferentially exposed cathode MnCo2O4Has a particle diameter of about 300nm, and is preferentially exposed to [111]]A crystal plane.
The above examples can be illustrated in many ways, and it is proved from a large amount of test data of the applicant that the octahedral morphology metal oxide can be successfully applied to the cathode side of the fuel cell within the range of the technical solution of the present invention.
Comparative example 1
Single cell 1: synthesizing MnCo by adopting citric acid-EDTA complexation method2O4Powder (particle size about 300nm, no preferential exposure crystal face) prepared by directly coating MnCo with a scraping method2O4The powder is prepared on Ni-YSZ/supported by an anode, and is roasted for 5 hours at 1100 ℃ in the air atmosphere, and the heating and cooling speed is 10 ℃/min, so that the battery 1 is obtained. The performance test condition of the cell 1 was that the atmosphere on the anode side was humidified hydrogen (100mL min)-1 3vol.％H2O--H2(at STP)), the atmosphere on the cathode side was air (100mL min)-1(at STP)), the test temperature was at 700-. Maximum output of battery 1 at 800, 750 and 700 deg.CThe output power density is respectively 850 mW cm, 590 mW cm and 320mW cm-2。
Example 10
Single cell 2: the preferential exposure obtained in example 9 was obtained by means of a coating method [111]]Crystal face MnCo2O4Preparing on Ni-YSZ/YSZ supported by the anode, roasting for 5 hours at 1100 ℃ in air atmosphere, and increasing and decreasing the temperature at the speed of 10 ℃/min to obtain the battery 2. The performance test condition of the cell 2 was that the atmosphere on the anode side was humidified hydrogen (100mL min)-1 3vol.％H2O--H2(at STP)), the atmosphere on the cathode side was air (100mL min)-1(at STP)), the test temperature was at 700-. The maximum output power density of the battery 2 at 800 ℃, 750 ℃ and 700 ℃ is 2030, 1550 and 1068mW cm respectively-2。

Claims (8)

1. A preparation method of spinel oxide with a preferred crystal face is characterized by comprising the following steps: the preparation method comprises the following steps: spinel oxide AxByOzPlacing the material in a calcining furnace, introducing a current of 1mA-10A, heating to 500-1300 ℃ in a certain calcining atmosphere, calcining for 1-300 h, and cooling to obtain the preferred crystal face spinel oxide; the calcining atmosphere is oxidizing atmosphere or inert atmosphere.
2. The production method according to claim 1, wherein the spinel oxide A isxByOzThe particle size of (A) is 1nm-5 μm; the gas of the oxidizing atmosphere is air, oxygen or a mixed gas of oxygen and inert gas; the inert atmosphere gas and the inert gas are independently selected from helium, nitrogen or argon; the heating and cooling rates are 0.01-100 ℃/min.
3. The method according to claim 1, wherein A is at least one of metal elements, B is at least one of metal elements, and at least one of A and B is a transition metal element of a fourth period; x has a value in the range of 0 to 3; y has a value in the range of 0 to 3, and the sum of x and y is 3, and z is 4.
4. A preferred crystal face spinel oxide prepared by the preparation method of claim 1, wherein the preferred crystal face spinel oxide is a regular octahedron with exposed [111] and/or [011] crystal faces; the grain size of the preferred crystal face spinel is 1nm-5 mu m.
5. A solid oxide fuel cell cathode comprising the preferential lattice plane spinel oxide of claim 4.
6. A method of making the solid oxide fuel cell cathode of claim 5, comprising the steps of:
(1) coating the spinel oxide with the preferred crystal face on an electrolyte of a solid oxide fuel cell by a screen printing method, a coating and scraping method, a tape casting method and a spin coating method to prepare a cathode blank;
(2) and (2) calcining the cathode blank obtained in the step (1) at the temperature of 600-1300 ℃ for 0.1-50 h to obtain the solid oxide fuel cell cathode.
7. The method according to claim 6, wherein the electrolyte is ZrO2Base electrolyte, CeO2A base electrolyte, an LSGM base electrolyte or Ba (Ce, Zr) O3A base electrolyte.
8. The use of the solid oxide fuel cell cathode of claim 5, wherein the cathode is stable for 1 to 40000h in the operating temperature range and the operating atmosphere of the solid oxide fuel cell; the working temperature range is 200-1000 ℃; the working atmosphere is an oxidizing atmosphere.
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