CN115832327A - Solid oxide fuel cell anode, preparation method thereof, single cell and electric pile - Google Patents
Solid oxide fuel cell anode, preparation method thereof, single cell and electric pile Download PDFInfo
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Abstract
The invention belongs to the field of SOFC (solid oxide fuel cell), and particularly relates to an SOFC anode prepared based on nickel foam, a preparation method, a single cell and a galvanic pile. The invention provides a solid oxide fuel cell anode which comprises foamed nickel and YSZ/NiO porous ceramic loaded on the foamed nickel. According to the invention, foam nickel is used as a carrier, and Ni-YSZ composite slurry is loaded on the foam nickel to prepare the SOFC anode by utilizing the characteristics of a large number of natural pores, good ductility and convenience in cutting into various shapes, so that the anode naturally has a large number of pores, good ductility and a formed Ni network; the SOFC anode has good mechanical property and electronic conductivity, and can meet different use requirements.
Description
Technical Field
The invention belongs to the field of solid oxide fuel cells, and particularly relates to a solid oxide fuel cell anode, a preparation method thereof, a single cell and a galvanic pile.
Background
A Solid Oxide Fuel Cell (SOFC) is a power generation device that can directly convert chemical energy in fuel into electrical energy. It has the advantages of high energy conversion efficiency, wide fuel selection range, no need of noble metal catalysis, all-solid-state structure and the like, and is considered to be a fuel cell with great development prospect. SOFCs generally consist of three parts, an anode, an electrolyte layer and a cathode. In order to reduce the ohmic internal resistance of the cell, the electrolyte layer, which is an oxygen ion conductor, is usually processed into a thin film, and in this case, it is necessary to use the anode or the cathode as a support structure of the SOFC.
Among a series of similar structures, the use of Ni-YSZ composite cermet as the anode support is currently the most common SOFC cell structure. Wherein, ni provides electron conductance and catalytic activity reaction sites for direct electrochemical oxidation or methane steam reforming; YSZ matches the coefficient of thermal expansion of the anode material to the most common electrolyte material today (8 YSZ) and extends ionic conduction to the reaction zone of the anode; in addition, YSZ acts as a structural support in the anode, giving the anode sufficient mechanical strength and preventing further agglomeration and growth of Ni in long-term high temperature working environments.
At present, the traditional preparation methods of the Ni-YSZ composite anode mainly comprise two methods: (1) dry pressing: pressing and molding Ni-YSZ or NiO-YSZ mixed powder in a steel mold with fixed specification, and then sintering and reducing to obtain a Ni-YSZ anode with a certain shape; (2) casting method: preparing mixed powder of Ni-YSZ or NiO-YSZ and the like into casting slurry, obtaining a Ni-YSZ anode film with a certain thickness by casting, and then cutting, sintering and reducing to obtain the Ni-YSZ anode with a regular shape. The disadvantages of these two methods for preparing Ni-YSZ anodes are mainly the following: 1. the porosity requirement of the anode can be met by adding a pore-forming agent, and the existence state (size, morphology, open pores or closed pores) of pores cannot be controlled; 2. the electron conductance of the anode depends on the formation of a Ni network, but this process cannot be controlled; 3. the support strength of the anode depends on the YSZ framework, but the formation of the YSZ framework can not be controlled; 4. the prepared Ni-YSZ metal ceramic composite anode has extremely poor ductility, and is difficult to be tightly attached to a mold due to inevitable fine unevenness in the subsequent battery sealing process, so that single battery cells are crushed under pressure or the battery leaks air.
Disclosure of Invention
The invention aims to overcome the problem that the anode air hole state, the Ni network and the YSZ framework state are uncontrollable in the prior art, and provides a solid oxide fuel cell anode prepared based on foamed nickel.
In order to achieve the above object, one of the objects of the present invention is to provide a solid oxide fuel cell anode comprising foamed nickel and YSZ/NiO porous ceramic supported on the foamed nickel.
Another object of the present invention is to provide a method for preparing an anode of a solid oxide fuel cell, comprising the steps of:
s1, obtaining pretreated foamed nickel;
s2, obtaining YSZ/NiO slurry;
s3, soaking YSZ/NiO slurry in the pretreated foamed nickel to obtain an NF/YSZ/NiO composite;
and S4, carrying out hot-pressing sintering on the NF/YSZ/NiO composite body in a protective gas atmosphere to obtain the solid oxide fuel cell anode.
It is a further object of the present invention to provide a solid oxide fuel cell anode, obtained by the above method.
The solid oxide fuel cell sequentially comprises an anode, an electrolyte layer and a cathode layer from bottom to top, wherein the anode is the solid oxide fuel cell anode, the solid oxide fuel cell anode is provided with an upper surface and a lower surface, and YSZ/NiO porous ceramics are loaded on the upper surface; wherein the upper surface is in contact with the electrolyte layer and the lower surface is remote from the electrolyte layer.
The fifth object of the present invention is to provide a stack comprising the solid oxide fuel cell.
Compared with the prior art, the invention has the following technical effects:
according to the invention, foam nickel is used as a carrier, and Ni-YSZ composite slurry is loaded on the foam nickel by utilizing the characteristics of a large number of natural air holes, good ductility and convenience in cutting into various shapes, so that the prepared solid oxide fuel cell anode has a large number of air holes, good ductility and a formed Ni network; the solid oxide fuel cell anode prepared by the method has good mechanical properties and good electronic conductivity, and can meet different use requirements.
Meanwhile, the technology provided by the invention is simple and is easy for large-scale production.
Description of the drawings:
FIG. 1 is a flow diagram of a process for making an anode for a solid oxide fuel cell in accordance with an embodiment of the present invention;
fig. 2 is a schematic structural view of a solid oxide fuel cell according to an embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the following embodiments, which are only used for illustrating the technical solution of the present invention and are not limited.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the use of the directional terms such as "upper" and "lower" are based on the orientation or positional relationship shown in the drawings and are used only for the convenience of describing the present application and for the simplicity of description, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed in a particular orientation, and be operated, and therefore should not be construed as limiting the present application.
In the present invention, YSZ means Y 2 O 3 Doped ZrO 2 (ii) a Wherein Y is 2 O 3 The doping concentration of (A) is 3-8mol%. When Y is 2 O 3 When the doping concentration of (2) is 3mol%, the molecular formula of YSZ is (Y) 2 O 3 ) 0.03 (ZrO 2 ) 0.97 Abbreviated as 3YSZ; when Y is 2 O 3 At a doping concentration of 8mol%, the molecular formula of YSZ is (Y) 2 O 3 ) 0.08 (ZrO 2 ) 0.92 Abbreviated as 8YSZ.
Foamed nickel: nickel Foam, abbreviated NF.
The invention provides a solid oxide fuel cell anode, which comprises foamed nickel and YSZ/NiO porous ceramic loaded on the foamed nickel;
preferably, the solid oxide fuel cell anode has an upper surface and a lower surface, and the loading of the YSZ/NiO porous ceramic decreases gradually from the upper surface to the lower surface.
Preferably, the face porosity of the solid oxide fuel cell anode is 10-30%;
preferably, the pore size of the pores in the solid oxide fuel cell anode is 0.5-4 μm, preferably 0.5-2 μm;
preferably, the polarization impedance of the solid oxide fuel cell anode is less than 3 Ω · cm 2 Preferably less than 1.5. Omega. Cm 2 。
FIG. 1 is a flow diagram of a process for preparing a solid oxide fuel cell anode according to an embodiment of the present invention; as shown in fig. 1, the present invention also provides a method for preparing an anode of a solid oxide fuel cell, comprising the steps of:
s1, obtaining pretreated foamed nickel;
s2, obtaining YSZ/NiO slurry;
s3, soaking YSZ/NiO slurry in the pretreated foamed nickel to obtain an NF/YSZ/NiO composite;
and S4, carrying out hot-pressing sintering on the NF/YSZ/NiO composite body under the atmosphere of protective gas to obtain the solid oxide fuel cell anode.
In the present invention, the oil stain on the surface of the nickel foam can be removed by a pretreatment, which may be known to those skilled in the art. Illustratively, the pre-processing comprises: firstly, carrying out ultrasonic treatment on foamed nickel in a sodium hydroxide solution, then carrying out ultrasonic treatment in an acetone solution, finally carrying out ultrasonic washing in ionized water and absolute ethyl alcohol in sequence, and finally drying under a vacuum condition.
In the present invention, the preparation method of the YSZ/NiO slurry can be well known to those skilled in the art. Illustratively, the preparation method may include: adding water, a dispersing agent and a binder into the mixture of the YSZ powder and the NiO powder, and then carrying out ball milling and mixing to obtain YSZ/NiO slurry.
In the present invention, preferably, in step S2, in the YSZ/NiO slurry, the mass ratio of YSZ to NiO is 1:1-1.8.
The inventor of the invention finds that the solid content of YSZ/NiO slurry is too low, which can cause that NiO/YSZ can not be effectively absorbed in the pore diameter of foam nickel; the solid content of YSZ/NiO slurry is too high, the viscosity of the slurry is increased, and NiO/YSZ cannot effectively enter into the pores of foamed nickel, so that the loading capacity is reduced. Preferably, the YSZ/NiO slurry has a solids content of 20 to 40wt%.
In the present invention, the particle size and specific surface area of the YSZ powder and NiO powder will affect the viscosity of the slurry, and thus the amount of YSZ/NiO slurry that enters the pores of the foamed nickel. Preferably, D of said YSZ 50 50-80nm, and 60-80m of specific surface area 2 (ii) in terms of/g. Further preferably, D of the NiO 50 50-80nm, and 60-80m specific surface area 2 /g。
In some preferred embodiments of the present invention, in step S3, the method of impregnation comprises: and repeatedly soaking one side of the foamed nickel in the YSZ/NiO slurry for 2-10 times, and drying the foamed nickel absorbing the slurry after each soaking.
Preferably, the method of impregnation comprises:
1) Weighing the mass of the pretreated foam nickel NF and recording the mass as M 0 ；
2) Dipping one surface of the foamed nickel in the slurry for 10-20min;
3) Drying the foam nickel NF absorbing the slurry, weighing again and recording as M 1 ；
4) Repeating steps 2) and 3);
5) Repeating the above steps until Mx (x is 1, 2, 3, 8230; x) and M 0 Reaches a predetermined value, and the impregnation process is ended.
Preferably, in the NF/YSZ/NiO composite body, the unit loading of the slurry is 0.03-0.3g/cm 2 (ii) a Preferably 0.05 to 0.1g/cm 2 The loading refers to the average loading of the slurry in the nickel foam.
The anode prepared by the invention takes the foam nickel as a supporting framework and loads NiO-YSZ porous ceramics. One side of the foamed nickel is NiO-YSZ porous ceramic based on a foamed nickel network structure, and the foamed nickel provides an excellent Ni conductive network and gaps, so that the anode support is endowed with sufficient electronic conductivity and porosity; the NiO-YSZ slurry pressed and sintered after slurry hanging firstly fills partial gaps of the foam nickel network to form a relatively flat and compact surface, which is beneficial to the subsequent screen printing process of an electrolyte layer, and secondly, YSZ is added, so that the NiO-YSZ slurry can be expanded to a reaction area of an anode through ion conduction, and the length of a three-phase interface is increased.
The other side of the foam nickel is not coated with slurry, so that the characteristics of high ductility, high porosity and good conductivity of the foam nickel are still kept, the effect of electron transmission can be born, the problem of crushing of a battery piece under pressure in the battery sealing process can be effectively solved, and meanwhile, the foam nickel can be tightly attached to a battery mold, so that the collection and the conduction of current between an anode and the battery mold are facilitated.
In the present invention, preferably, in step S4, the conditions of the hot press sintering include: the temperature is 900-1000 deg.C, the time is 1-5h, and the pressure is 10-50MPa.
And hot-pressing sintering is carried out in a protective gas atmosphere, so that the oxidation of the foamed nickel can be reduced, and the purpose of the hot-pressing sintering is to obtain a relatively flat surface as far as possible so as to prepare for the subsequent silk-screen process.
The protective atmosphere may be known to the person skilled in the art, and may be, for example, a nitrogen atmosphere and/or an inert gas atmosphere.
Preferably, the YSZ is 3-8mol% yttria stabilized zirconia.
The invention also provides a solid oxide fuel cell anode prepared by the method.
Preferably, the solid oxide fuel cell anode comprises foamed nickel and YSZ/NiO porous ceramic supported on the foamed nickel.
Further preferably, the solid oxide fuel cell anode has an upper surface and a lower surface, and the loading of the YSZ/NiO porous ceramic decreases gradually from the upper surface to the lower surface.
The aperture of the solid oxide fuel cell anode is 0.5-1.5 μm.
Preferably, the face porosity of the solid oxide fuel cell anode is 10-25%.
Preferably, the polarization impedance of the solid oxide fuel cell anode is less than 3 Ω · cm 2 。
The solid oxide fuel cell anode provided by the invention has the functions of an anode supporting layer and an anode functional layer, namely, the side without loading porous ceramics has the function of the anode supporting layer, and the side loading the porous ceramics has the function of the anode functional layer. The three-phase interface can be provided, and an electronic conductance and catalytic activity reaction site is provided for direct electrochemical oxidation or methane steam reforming; can also be used as a supporting structure of the solid oxide fuel cell
Fig. 2 is a schematic structural diagram of a solid oxide fuel cell according to an embodiment of the present invention, and as shown in fig. 2, the present invention further provides a solid oxide fuel cell 10, which includes, in order from bottom to top, an anode 11, an electrolyte layer 12, and a cathode layer 13, where the anode is the aforementioned solid oxide fuel cell anode, the solid oxide fuel cell anode has an upper surface 11a and a lower surface 11b, and YSZ/NiO porous ceramics are supported on the upper surface 11 a; wherein the upper surface 11a is in contact with the electrolyte layer 12 and the lower surface 11b is remote from the electrolyte layer.
Preferably, the thickness of the anode is 500-2000 μm, which may be 1000 μm, for example.
Preferably, the thickness of the electrolyte layer is 5 to 50 μm, preferably 10 to 30 μm, more preferably 10 μm.
Preferably, the thickness of the cathode layer is 5-50 μm, preferably 10-30 μm, more preferably 20 μm.
The invention also provides a galvanic pile which comprises the single solid oxide fuel cell.
The present invention will be described in detail with reference to the following examples.
In the following examples, the Nickel Foam (NF) has a thickness of 1mm and a porosity of >95%.
In the following examples, the three-point bending strength of the anode was measured by a universal material testing machine;
the conductivity of the anode is measured by a digital universal meter (Keithley-DMM 6500) by adopting a four-probe method, the measurement temperature is 750 ℃, and hydrogen reduction is needed before the measurement;
measuring the polarization impedance of the anode by using an electrochemical workstation (DH 7001A), measuring by adopting a two-probe method, wherein the measurement temperature is 750 ℃, and hydrogen reduction is needed before the measurement;
the viscosity of the NiO-YSZ composite slurry was measured by a rotational viscometer (NDJ-1);
after the foamed nickel is sintered by hot pressing, the surface porosity and the pore size of one surface of the loaded porous ceramic are measured by a metallographic microscope (IMAS-2000) and are obtained by an Image-J software test. The formula for calculating the face porosity is: face porosity = face pore size/area; .
Example 1
S1, pretreatment of foamed nickel:
cutting foamed nickel into square (side length is10 cm), then carrying out ultrasonic treatment on the foamed nickel in 1mol/L sodium hydroxide solution for 30min, then carrying out ultrasonic treatment in acetone solution for 10min, finally carrying out ultrasonic washing in ionized water and absolute ethyl alcohol for 10min in sequence, drying at 60 ℃ under the vacuum condition, weighing the foamed nickel with the weight of 2.50g, and recording the weight as M 0 And then standby.
S2, preparing NiO-YSZ composite slurry:
in NiO powder (D) 50 Is 50nm, and has a specific surface area of 60m 2 /g) 8YSZ powder (D) 50 Is 50nm, and has a specific surface area of 60m 2 Adding polyvinyl alcohol (PVA), hydroxymethyl cellulose (CMC) and deionized water into the mixture, wherein the solid content is 30 percent, and the mass ratio of 8YSZ to NiO is 1:1.5, PVA is used in an amount of 1wt% based on the total weight of the powder (the total weight of NiO powder and 8YSZ powder), and CMC is used in an amount of 0.4wt% based on the total weight of the powder.
S3, preparing NF/YSZ/NiO complex
Soaking one surface (not less than 1/3 of the position) of the treated foam nickel in the NiO-YSZ composite slurry, taking out the foam nickel after 10min, placing the foam nickel on a tray, drying the foam nickel in an oven, weighing the mass of the foam nickel at the moment, recording the mass as M1, and repeating the process for 7 times repeatedly, wherein the mass and the performance of the foam nickel after each slurry hanging are shown in Table 1;
s4, preparing the solid oxide fuel cell anode by hot-pressing sintering:
and (3) carrying out hot-pressing sintering on the foamed nickel after the slurry coating is finished in a nitrogen atmosphere, wherein the sintering temperature is 1000 ℃, the heat preservation time is 1h, and the pressure is 30MPa, so as to obtain the solid oxide fuel cell anode.
Table 1:
as can be seen from table 1: along with the increase of the times of slurry hanging, the load capacity of YSZ/NiO in the foam nickel is also increased slowly, and the increasing speed of the load capacity is gradually reduced; when X =5 (i.e., at the time of 5 th sizing), there is almost no significant increase in the amount of YSZ/NiO loaded, because as the sizing frequency increases, the pores of the nickel foam are filled, the pore size gradually decreases, and the adsorption capacity to the slurry gradually decreases. When the pore diameter of the surface of the foamed nickel is reduced to a certain degree, the foamed nickel can not adsorb slurry any more, so that the loading capacity tends to be stable.
With the increase of slurry coating times, the surface porosity and pore size of the anode of the solid oxide fuel cell are continuously reduced after hot-pressing sintering and hydrogen reduction. This demonstrates that the porosity and pore size of the anode can be adjusted by controlling the number of times of slurry hanging.
When the number of times of the slurry hanging is less than 5 times, the electronic conductivity of the anode hardly changes with the increase of the number of times of the slurry hanging, which shows that the anode is endowed with extremely high electronic conductivity by adopting the foamed nickel as the base material. While anodes (1X 10) were prepared in a conventional manner (casting YSZ-NiO slurry or dry pressing YSZ-NiO powder, then sintering the cast film or green compact) 5 About S/m).
When the slurry coating times reach 5 times, the polarization impedance of the anode is continuously reduced along with the increase of the slurry coating times until the polarization impedance tends to be stable. This is because, when the number of times of slurry coating is small, the number of three-phase interfaces on the anode is insufficient, the catalytic ability for hydrogen is insufficient, and the transport ability for electrons and oxygen ions is insufficient, so that the polarization impedance is large, and even the polarization impedance value cannot be measured at all. And when X is more than or equal to 5, the foamed nickel cannot adsorb more slurry due to the reduction of pores, the porosity and the pore size of the anode are not changed obviously, and the stool and urine of the polarization impedance tend to be stable.
Examples 2 to 3 and comparative examples 1 to 2
Solid oxide fuel cell anodes were prepared according to the method used in example 1, except that the slurries in examples 2 and 3 had solids contents of 20wt% and 40wt%, respectively, and the slurries in comparative examples 1 and 2 had solids contents of 10wt% and 50wt%, respectively, as shown in table 2.
Table 2 shows the loading, viscosity and polarization impedance of the slurries with different solid contents after 5 times of slurry hanging.
Table 2:
as can be seen from table 5, as the solid content of the slurry increases, the viscosity of the slurry as a whole increases, and the load amount tends to increase and then decrease. This is because NiO/YSZ is not effectively adsorbed in the pore size of the nickel foam when the viscosity of the slurry is low, and it does not well enter the pores of the nickel foam due to the surface tension when the viscosity of the slurry is too high, resulting in a decrease in the loading amount. This also explains why the polarization resistance of the anode is decreased first and then increased because the triphasic interface length of the anode is changed as the load amount is changed.
Example 4 and comparative examples 3 to 5
The solid oxide fuel cell anode was fabricated by referring to the method adopted in example 1, except that the temperature of the hot press sintering in example 4 was 900 deg.c, and the temperatures of the hot press sintering in comparative examples 3, 4, and 5 were 800 deg.c, 1100 deg.c, and 1200 deg.c, respectively.
Table 3 shows the face porosity and pore size of anodes prepared at different hot press sintering temperatures.
Table 3:
as can be seen from table 3, the surface porosity and pore size of the anode both decrease with increasing hot press sintering temperature. When the hot press sintering temperature reaches 1100-1200 c, the anode is almost completely densified due to the high temperature of the hot press sintering, which obviously does not meet the SOFC requirement that the anode must possess sufficient porosity. When the temperature is reduced to 800 ℃, the surface porosity of the anode is too high, the length of a three-phase interface is influenced, and the polarization impedance of the anode is extremely high.
Examples 5 to 6 and comparative examples 6 to 7
A solid oxide fuel cell anode was prepared by referring to the method used in example 1, except that the mass ratio of 8YSZ and nickel oxide was as shown in table 4.
Table 4 gives the different NiO: the viscosity of the slurry prepared by 8YSZ mass ratio and the load capacity after slurry hanging; and the face porosity, pore size, and polarization resistance of anodes prepared under different mass ratios.
TABLE 4
As can be seen from table 4, when the solid content is fixed, changing the mass ratio of nickel oxide and 8YSZ in the slurry does not significantly affect the viscosity of the slurry, and thus does not affect the slurrying process.
It can also be seen from table 4 that as the proportion of nickel oxide increases, the surface porosity and pore size of the anode increase continuously, because a part of the anode porosity comes from the process of reducing NiO by hydrogen to form Ni, so as the mass of 8YSZ increases, the surface porosity and pore size of the sintered anode increase continuously. This leads to a first reduction in the polarization resistance of the anode, since more and larger pores facilitate gas entry and exchange, but as nickel oxide: the mass ratio of 8YSZ reaches 1:2, the porosity of the anode is too large, the content of Ni is reduced along with the increase of the content of 8YSZ, and the length of a three-phase interface is reduced due to double factors, so that the polarization resistance of the anode is increased.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A solid oxide fuel cell anode, characterized in that the solid oxide fuel cell anode comprises foamed nickel and YSZ/NiO porous ceramic supported on the foamed nickel;
preferably, the solid oxide fuel cell anode has an upper surface and a lower surface, and the loading of the YSZ/NiO porous ceramic decreases gradually from the upper surface to the lower surface.
2. The solid oxide fuel cell anode of claim 1, wherein the solid oxide fuel cell anode has a face porosity of 10-30%;
preferably, the pore diameter of pores in the solid oxide fuel cell anode is 0.5-4 μm;
preferably, the polarization impedance of the solid oxide fuel cell anode is less than 3 Ω · cm 2 Preferably less than 1.5. Omega. Cm 2 。
3. A method of making a solid oxide fuel cell anode, comprising the steps of:
s1, obtaining pretreated foamed nickel;
s2, obtaining YSZ/NiO slurry;
s3, soaking YSZ/NiO slurry in the pretreated foamed nickel to obtain an NF/YSZ/NiO composite;
and S4, carrying out hot-pressing sintering on the NF/YSZ/NiO composite body under the atmosphere of protective gas to obtain the solid oxide fuel cell anode.
4. The method of claim 3, wherein in step S2, the mass ratio of YSZ to NiO in the YSZ/NiO slurry is 1:1 to 1.8;
preferably, the YSZ/NiO slurry has a solid content of 20-40%;
preferably, D of said YSZ 50 50-80nm, and 60-80m of specific surface area 2 /g；
Preferably, D of the NiO 50 Is 50-80nm, ratioThe surface area is 60-80m 2 /g；
Preferably, the YSZ is 3-8mol% yttria doped zirconia.
5. The method according to claim 3 or 4, characterized in that in step S3, the method of impregnation comprises: and repeatedly soaking one side of the foamed nickel in the YSZ/NiO slurry for 2-10 times, and drying the foamed nickel absorbing the slurry after each soaking.
6. The method of any of claims 3-5, wherein the NF/YSZ/NiO composite has a unit loading of the slurry of 0.03 to 0.3g/cm 2 (ii) a Preferably 0.05 to 0.1g/cm 2 。
7. The method according to any one of claims 3 to 6, wherein in step S4, the conditions of the hot press sintering comprise: the temperature is 900-1000 ℃, the time is 1-5h, and the pressure is 10-50MPa.
8. A solid oxide fuel cell anode, prepared by the method of any one of claims 3 to 7;
preferably, the solid oxide fuel cell anode comprises foamed nickel and YSZ/NiO porous ceramic supported on the foamed nickel;
preferably, the solid oxide fuel cell anode has an upper surface and a lower surface, and the loading of the YSZ/NiO porous ceramic decreases gradually from the upper surface to the lower surface.
9. A solid oxide fuel cell comprising, in order from bottom to top, an anode (11), an electrolyte layer (12) and a cathode layer (13), wherein the anode is the solid oxide fuel cell anode of claim 1 or 8, the solid oxide fuel cell anode having an upper surface (11 a) and a lower surface (11 b), the upper surface (11 a) being loaded with YSZ/NiO porous ceramic; wherein the upper surface (11 a) is in contact with the electrolyte layer (12) and the lower surface (11 b) is remote from the electrolyte layer.
10. A stack comprising the solid oxide fuel cell of claim 9.
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