CN113381041B - Electrode-supported solid oxide fuel cell and preparation method thereof - Google Patents

Abstract

The invention discloses an electrode supporting type solid oxide fuel cell and a preparation method thereof, belonging to the technical field of fuel cells. The fuel cell comprises a porous ceramic support prepared by a phase inversion method; the porous ceramic support is prepared from a raw material containing 3-5mol% of Y ₂ O ₃ Y of (A) is ₂ O ₃ ‑ZrO ₂ Mixing; the porous ceramic support is impregnated with an electrode material. By adding 3-5mol% of Y ₂ O ₃ Y of (A) is ₂ O ₃ ‑ZrO ₂ The mixture is used as the main raw material for preparing the porous ceramic support and is combined with a dipping electrode to replace an electronic conductive phase and 8mol percent of Y adopted in the prior art ₂ O ₃ Y of (A) is ₂ O ₃ ‑ZrO ₂ The method for preparing the support framework by the mixture can effectively improve the integral breaking strength of the support prepared by the phase inversion method and the fuel cell containing the support. The preparation method of the fuel cell is simple, easy to operate and suitable for industrial production.

Description

An electrode-supported solid oxide fuel cell and its preparation method

technical field

The invention relates to the technical field of fuel cells, in particular to an electrode-supported solid oxide fuel cell and a preparation method thereof.

Background technique

Solid oxide fuel cell (SOFC) is a non-combustion chemical energy conversion device with an all-solid ceramic structure. The biggest difference from traditional batteries is that fuel cells are power generation equipment rather than energy storage equipment. The fuel has wide applicability and power generation. The process can also provide high-grade waste heat energy, which has broad application prospects in distributed energy supply and combined heat and power generation. Its unique advantages combined with low-carbon clean energy such as natural gas and biomass will provide important support for sustainable development.

There are three main structural designs of SOFC, namely, electrolyte-supported, electrode-supported, and metal-supported. Reducing the operating temperature is the mainstream of SOFC research in recent years, and the focus of exploration is to use electrode support to realize thin electrolyte. The fuel electrode of the fuel-supported SOFC is most commonly used as a nickel-based composite material. During the oxidation-reduction process of a single cell, the volume expansion or contraction of the nickel metal phase will lead to cracking and delamination of the battery, resulting in poor mechanical strength of the battery. decrease, seriously affecting the performance and long-term stability of the battery; for the air-electrode-supported SOFC, the chemical compatibility of the electrolyte/air-electrode interface and the densification of the electrolyte film are the key issues in the preparation of the air-electrode-supported SOFC, which involves Two conflicting issues of sintering temperature. The sintering temperature of the electrolyte often does not match the sintering temperature of the air electrode. Although high temperature sintering can promote the densification of the electrolyte film, at the same time, high temperature will accelerate the chemical reaction or element diffusion between the electrolyte and the air electrode.

For example, the commonly used zirconia-stabilized yttrium oxide (YSZ) electrolyte and air electrode support material La _0.8 Sr _0.2 MnO _3-δ -Y _0.15 Zr _0.85 O _2-δ (LSM-YSZ), sintering at high temperature usually produces insulating impurities ( Such as La ₂ Zr ₂ O ₇ , SrZrO ₃ ) hinder the conduction of electrons and ions, and high temperature sintering will also make the LSM grains too large, the specific surface area and activity will be greatly reduced, and the air polarization resistance will be increased. Lowering the sintering temperature can improve the chemical compatibility of the electrolyte and the air electrode, but it is challenging to obtain a dense electrolyte film and cannot guarantee sufficient mechanical strength.

The research so far has generally focused on the preparation and testing of button batteries, and the focus is on the improvement of electrochemical performance. There are few reports on battery strength, flatness, and large-area battery preparation. The battery must meet certain requirements in terms of flatness and strength in order to withstand the pressure test of sealing and current collection during the test process, so improving the mechanical strength of the battery is also one of the factors that must be considered during preparation.

The support prepared by the phase inversion casting method can effectively solve the problem of mass transfer resistance, and shows good gas transfer performance on the oxygen permeable membrane and SOFC. However, it has the following problems: the fracture strength is low, especially the characteristics of finger-shaped macropores formed by solvent extraction by phase inversion method, so that the strength decrease in the X direction is more obvious.

In view of this, the present invention is proposed.

Contents of the invention

One of the objectives of the present invention is to provide an electrode-supported solid oxide fuel cell, which not only has good strength performance, but also has good gas transmission performance.

The second object of the present invention is to provide a method for preparing the above-mentioned electrode-supported solid oxide fuel cell, which is simple, easy to operate, and suitable for industrial production.

The present invention can be realized like this:

In a first aspect, the present invention provides an electrode-supported solid oxide fuel cell, which includes a porous ceramic support prepared by a phase inversion method; the raw materials for preparing the porous ceramic support include a first ceramic powder, a first ceramic The powder is a Y ₂ O ₃ -ZrO ₂ mixture containing 3-5 mol% of Y ₂ O ₃ ; the porous ceramic support body is impregnated with electrode materials.

In an optional embodiment, the raw materials for the preparation of the porous ceramic support further include a pore-forming agent.

In an optional embodiment, the raw materials for the preparation of the porous ceramic support further include additives including a binder, a dispersant and an organic solvent.

Further, the electrode-supported solid oxide fuel cell further includes a porous layer, which is used to be deposited on one surface of the porous ceramic support in the thickness direction.

In an optional embodiment, the raw material for preparing the porous layer includes a second ceramic powder, and the second ceramic powder includes a first scandia-stabilized zirconia and a second scandia-stabilized zirconia, and the second scandia-stabilized zirconia The zirconium oxide is obtained by calcining the first scandia-stabilized zirconium oxide under the condition of 950-1100° C. for 1.5-2.5 hours.

In an optional embodiment, the raw materials for preparing the porous layer further include a pore-forming agent and additives including a binder, a dispersant and an organic solvent.

Further, the electrode-supported solid oxide fuel cell further includes an electrolyte layer, and the electrolyte layer is used to be deposited on the surface of the porous layer on the side away from the porous ceramic support.

In an optional embodiment, the raw materials for the preparation of the electrolyte layer include the second ceramic powder and additives including a binder, a dispersant and an organic solvent.

Further, the electrode-supported solid oxide fuel cell further includes a porous electrode, which is used to be deposited on the surface of the electrolyte layer on a side away from the porous layer.

In an optional embodiment, when the porous electrode is a porous anode, the raw materials for preparing the porous anode include anode powder and a pore-forming agent.

In an optional embodiment, when the porous electrode is a porous cathode, the raw materials for preparing the porous cathode include cathode powder and a pore-forming agent.

In an optional embodiment, the cathode powder includes (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ powder and a second ceramic powder.

In an alternative embodiment, both the porous ceramic support and the porous layer are impregnated with an electrode material of opposite polarity to the porous electrode.

In an optional embodiment, when the porous electrode is an anode electrode, the electrode material used for impregnation includes at least one of La _0.8 Sr _0.2 Co _0.5 Fe _0.5 O _3-δ and (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ One, when the porous electrode is the cathode electrode, the electrode material used for impregnation includes SrFe _0.75 Mo _0.25 O _3-δ , La _1-x Sr _x Ni _0.4 Fe _0.6 O _3-δ or La _1-x Sr _x Ni _0.6 At least one of Fe _0.4 O _3-δ , wherein the value of x in La _1-x Sr _x Ni _0.4 Fe _0.6 O _3-δ and La _1-x Sr _x Ni _0.6 Fe _0.4 O _3-δ is greater than Any value between 0 and less than 1.

In the second aspect, the present invention provides a method for preparing an electrode-supported solid oxide fuel cell according to any one of the foregoing embodiments, comprising the following steps: preparing a porous ceramic support from raw materials for preparing a porous ceramic support by a phase inversion method, and The porous ceramic support is impregnated with electrode material.

Further, it also includes: depositing a porous layer on one surface of the porous ceramic support in the thickness direction.

Further, it also includes: depositing an electrolyte layer on the surface of the porous layer to be deposited.

Further, it also includes: depositing a porous electrode on the surface to be deposited of the electrolyte layer.

Further, it also includes: jointly impregnating the porous ceramic support body and the porous layer with an electrode material whose polarity is opposite to that of the porous electrode, followed by calcining.

The beneficial effects of the application include:

This application _replaces the _{electronically conductive phase} and _8mol % Y ₂ O ₃ Y ₂ O ₃ -ZrO ₂ mixture to prepare the support body skeleton, can effectively improve the overall fracture strength of the support body prepared by the phase inversion method and the fuel cell containing the above support body. The preparation method of the fuel cell is simple and easy to operate, and is suitable for industrial production.

Description of drawings

In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention, and thus It should be regarded as a limitation on the scope, and those skilled in the art can also obtain other related drawings based on these drawings without creative work.

Fig. 1 is the scanning electron micrograph of the cross-section of the cathode supported SOFC provided by Example 1 of the present application;

Fig. 2 is the scanning electron micrograph of the section of the porous layer in the cathode-supported SOFC that the embodiment 1 of the present application provides;

3 is a scanning electron micrograph of the surface of the electrolyte layer in the cathode-supported SOFC provided in Example 1 of the present application;

Fig. 4 is a scanning electron microscope image of the surface of the porous ceramic support in the cathode-supported SOFC provided in Example 1 of the present application.

Icons: 1-porous ceramic support; 2-porous layer; 3-electrolyte layer; 4-porous electrode.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

The electrode-supported solid oxide fuel cell provided by the present application and its preparation method are described in detail below.

The present application proposes an electrode-supported solid oxide fuel cell, which includes a porous ceramic support prepared by a phase inversion method; the raw material for the preparation of the porous ceramic support includes a first ceramic powder containing _{3-5 mol% Y 2 O 3 -ZrO 2 mixture ;} the porous ceramic support is impregnated with electrode material.

Wherein, the content of Y ₂ O ₃ in the Y ₂ O ₃ -ZrO ₂ mixture can be 3mol%, 3.5mol%, 4mol%, 4.5mol% or 5mol%, etc., and can also be any other value within the range of 3-5mol% . Taking the content of Y ₂ O ₃ in the Y ₂ O ₃ -ZrO ₂ mixture as 3 mol% as an example, the Y ₂ O ₃ -ZrO ₂ mixture can be referred to as 3YSZ ceramic powder.

By using the Y ₂ O ₃ -ZrO ₂ mixture containing 3-5 mol% Y ₂ O ₃ as the main preparation raw material of the porous ceramic support and combining impregnated electrodes to replace the electronically conductive phase and 8 mol% of the prior art The method for preparing the support body skeleton from the Y ₂ O ₃ -ZrO ₂ mixture of Y ₂ O ₃ can effectively improve the overall fracture strength of the support body prepared by the phase inversion method and the fuel cell containing the above support body.

The above-mentioned porous ceramic support body has a plurality of through holes in its thickness direction, and the through holes are substantially in the form of straight holes.

For reference, the thickness of the porous ceramic support in the present application may be 600-800 μm, such as 600 μm, 650 μm, 700 μm, 750 μm or 800 μm.

In an optional embodiment, the particle size of the above-mentioned first ceramic powder can be 0.1-1 μm, such as 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm or 1 μm, etc., and the specific surface area of the first ceramic powder can be 8 -15m ² /g, such as 8m ² /g, 10m ² /g, 12m ² /g or 15m ² /g, etc.

The first ceramic powder having the above-mentioned particle size and specific surface area is more conducive to obtaining a porous ceramic support body with better mechanical properties than the first ceramic powder having a particle size and specific surface area outside the above-mentioned range.

Further, the raw materials for the preparation of the above-mentioned porous ceramic support may also include a pore-forming agent.

For reference, the amount of the pore-forming agent added is 5-15wt% of the raw materials for the preparation of the porous ceramic support, such as 5wt%, 8wt%, 10wt%, 12wt% or 15wt%, preferably 5-10wt%, such as 5wt% %, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%, etc.

Further, the raw materials for the preparation of the above-mentioned porous ceramic support may also include additives including binders, dispersants and organic solvents.

For reference, in the raw materials for the preparation of the porous ceramic support, the mass ratio of the binder, the dispersant and the organic solvent may be 3-5:0.5-1.5:18-22, preferably 4:1:20.

The ratio of the total mass of the first ceramic powder and the pore former to the mass of the additive may be 1:1-3, preferably 1:1.5-2, such as 1:1.5, 1:1.8 or 1:2.

Further, the electrode-supported solid oxide fuel cell provided in the present application further includes a porous layer, which is used to be deposited on one surface of the porous ceramic support in the thickness direction.

For reference, the thickness of the porous layer may be 25-35 μm, such as 25 μm, 28 μm, 30 μm, 32 μm or 35 μm.

The raw materials for the preparation of the above porous layer include the second ceramic powder, the second ceramic powder includes the first scandia-stabilized zirconia and the second scandia-stabilized zirconia, the second scandia-stabilized zirconia is passed through the first scandium oxide The stabilized zirconia is obtained by calcining at 950-1100° C. for 1.5-2.5 hours, preferably the zirconia stabilized by the first scandium oxide is calcined at 1000° C. for 2 hours.

For ease of understanding, the following content abbreviates the first scandia-stabilized zirconia as SSZ, and abbreviates the second scandia-stabilized zirconia as SSZ-t, wherein, t represents the calcination temperature, for example, when the second scandia-stabilized zirconia When zirconia is obtained by calcining the first scandia-stabilized zirconia at 1000°C for 2 hours, the second scandia-stabilized zirconia is abbreviated as SSZ-1000.

In an optional embodiment, in the second ceramic powder, the mass ratio of SSZ and SSZ-t may be 2:8-3:7, such as 2:8, 2.5:7.5 or 3:7.

It is worth noting that the SSZ and SSZ-t contained in the second ceramic powder can change the sintering characteristics of the ceramic powder. If only SSZ is used as the second ceramic powder, it will lead to cracking and fracture during the sintering process. , by mixing SSZ-t after SSZ has been calcined at high temperature with SSZ, the second ceramic powder can have good sintering shrinkage performance.

Further, the raw materials for the above porous layer may also include a pore forming agent and additives including a binder, a dispersant and an organic solvent.

In an optional embodiment, in the raw materials for the preparation of the porous layer, the amount of the pore-forming agent added is 5-10wt% of the second ceramic powder, such as 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt% %Wait. The ratio of the total mass of the second ceramic powder and the pore former to the mass of the binder and the dispersant may be 100:20-30:2-3. Here, the second ceramic powder and the pore-forming agent are jointly defined as the porous layer powder, and the amount of the binder is 20-30wt% of the porous layer powder, such as 20wt%, 25% or 30wt%, and the dispersant The dosage is 2-3wt% of the porous layer powder, such as 2wt%, 2.5wt% or 3wt%.

In an optional embodiment, in the present application, the porosity of the porous ceramic support body and the porous layer as a whole is 25-35%.

Further, the electrode-supported solid oxide fuel cell provided in the present application further includes an electrolyte layer, and the electrolyte layer is used to be deposited on the surface of the porous layer on the side away from the porous ceramic support.

For reference, the thickness of the electrolyte layer may be 10-20 μm, such as 10 μm, 12 μm, 15 μm, 18 μm or 20 μm. The density of the electrolyte layer is preferably not lower than 95%.

In an optional embodiment, the raw materials for the preparation of the electrolyte layer also include the second ceramic powder and additives including a binder, a dispersant and an organic solvent. For ease of distinction, the second ceramic powder in the preparation raw materials of the electrolyte layer will be referred to as the electrolyte layer powder below.

In the preparation raw materials of the electrolyte layer, the mass ratio of the second ceramic powder (electrolyte layer powder) to the binder and the dispersant may be 100:20-30:2-3. That is, the amount of the binder is 20-30wt% of the electrolyte layer powder, such as 20wt%, 25% or 30wt%, and the amount of the dispersant is 2-3wt% of the electrolyte layer powder, such as 2wt%, 2.5 wt% or 3wt%, etc.

Further, the electrode-supported solid oxide fuel cell provided in the present application further includes a porous electrode, which is used to be deposited on the surface of the electrolyte layer on the side away from the porous layer. The porous electrode can be configured as a porous anode or a porous cathode as required.

For reference, the thickness of the porous electrode may be, for example, 25-35 μm, such as 25 μm, 28 μm, 30 μm, 32 μm or 35 μm.

In an optional embodiment, when the porous electrode is a porous anode, the raw materials for preparing the porous anode include anode powder and a pore-forming agent.

Wherein, the anode powder may include nickel oxide and the second ceramic powder, and the nickel oxide may also be replaced by other anode materials as required.

For reference, in the preparation raw materials of the porous anode, the mass ratio of nickel oxide, SSZ to SSZ-t and the pore-forming agent can be 18-22:3-5:15-17:0.8-1.2, preferably 20:4: 16:1.

Further, the raw materials for the above-mentioned porous anode can also include a binder solution, and the mass ratio of the binder solution to the anode powder can be 80-100:100, such as 80:100, 85:100, 90:100, 95 :100 or 100:100 etc.

In an optional embodiment, when the porous electrode is a porous cathode, the raw materials for preparing the porous cathode include cathode powder and a pore-forming agent.

Wherein, the cathode powder includes (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ powder and the second ceramic powder.

For reference, in the raw materials for porous cathode preparation, the mass ratio of (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ powder, SSZ to SSZ-t, and pore-forming agent can be 18-22:3-5:15-17 :0.8-1.2, preferably 20:4:16:1.

Further, the raw materials for the preparation of the above-mentioned porous cathode also include a binder solution, and the mass ratio of the binder solution to the cathode powder can be 80-100:100, such as 80:100, 85:100, 90:100, 95: 100 or 100:100 etc.

In an optional embodiment, the binder solution used in the preparation raw materials of the porous anode and the porous cathode can be ethyl cellulose solution. The binder solvent can be prepared in the following manner: weigh 5 g of ethyl cellulose, add 10 mL of absolute ethanol to dissolve it, then add 40 g of terpineol and 5 g of triethanolamine, and stir until the absolute alcohol is completely volatilized.

In an optional embodiment, the pore-forming agent used in the porous ceramic support body, porous layer and porous electrode of the present application all includes at least one of soluble starch, graphite, spherical carbon powder and polymethyl methacrylate microspheres , preferably including at least one of graphite and polymethylmethacrylate microspheres. It can be understood that: the pore-forming agents used in the porous ceramic support body, porous layer and porous electrode can be selected from the same material or different materials.

In addition, the binders, dispersants and organic solvents used in this application can be the corresponding substances commonly used in this field, and there is no excessive limitation here.

In an optional embodiment, in this application, in addition to the porous ceramic support being impregnated with the electrode material, the porous layer is also impregnated with the electrode material, and the impregnated electrode material is opposite in polarity to the porous electrode. In a specific operation, the porous ceramic support body and the porous layer may be impregnated with the electrode material as a whole.

In an optional embodiment, when the porous electrode is an anode electrode, the electrode material used for impregnation may include, for example, La _0.8 Sr _0.2 Co _0.5 Fe _0.5 O _3-δ and (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ At least one of, when the porous electrode is a cathode electrode, the electrode material used for impregnation may include, for example, SrFe _0.75 Mo _0.25 O _3-δ , La _1-x Sr _x Ni _0.4 Fe _0.6 O _3-δ or La _{1- x} At least one of Sr _x Ni _0.6 Fe _0.4 O _3-δ , among them, x in La _1-x Sr _x Ni _0.4 Fe _0.6 O _3-δ and La _1-x Sr _x Ni _0.6 Fe _0.4 O _3-δ The value can be any value greater than 0 and less than 1.

Correspondingly, the present application also provides a method for preparing the above-mentioned electrode-supported solid oxide fuel cell, which includes the following steps: preparing the porous ceramic support from raw materials for preparing the porous ceramic support by a phase inversion method.

For reference, the preparation of the porous ceramic support may include: ball milling and casting the mixture of the first ceramic powder, pore-forming agent and additives in the preparation raw materials of the porous ceramic support to obtain a green body. The green body is phase-inverted in a non-solvent, fully cured and then dried. Subsequent sintering and removal of binder and pore formers.

Preferably, the first ceramic powder and pore-forming agent can be wet-milled according to the ratio to obtain a YSZ-pore-forming agent mixed powder, and then the YSZ-pore-forming agent mixed powder and additives can be ball-milled. The above ball milling process can be carried out in a planetary ball mill, and the gray slurry can be obtained after ball milling for 12-24 hours. The gray slurry can be casted by a casting machine to obtain a green body. For reference, the thickness of the green body may be 0.7-1.2mm.

Subsequently, the green body is immediately put into a non-solvent for phase inversion. Wherein, the non-solvent may be deionized water, and the phase inversion time may be 12-24h.

After phase inversion, the green body is completely cured, then dried at 60-90°C, and cut into discs with a diameter of 15-25mm.

Subsequently, put the above wafer into a high-temperature furnace at a heating rate of 1-5°C/min (such as 1°C/min, 2°C/min, 3°C/min, 4°C/min or 5°C/min, etc.) Raise the temperature to 800-1200°C (such as 800°C, 900°C, 1000°C, 1100°C or 1200°C, etc.), keep it warm for 1-3h, and then at 3-5°C/min (such as 3°C/min, 3.5°C/min, 4°C/min, 4.5°C/min or 5°C/min, etc.) to 10-35°C (room temperature), thereby discharging the binder and pore-forming agent, and preparing a porous ceramic support.

In the above process, the green body is heated up as slowly as possible, so that the binder, dispersant and pore-forming agent in the green body can be discharged slowly, which can prevent the green body from breaking, delamination, etc., and improve the shape of the green body. Rate. Keeping warm at a temperature of 800-1200°C can further promote the complete decomposition and discharge of the binder and plasticizer in the green body; continue to cool down at an appropriate speed to ensure that the stress of the green body is released evenly, and prevent the green body from being damaged by excessive cooling. Body cracking and bending problems.

Further, a porous layer is deposited on one surface of the porous ceramic support in the thickness direction.

For reference, the preparation of the porous layer may include: mixing the second ceramic powder in the preparation raw materials of the porous layer with the pore-forming agent, and then performing ball milling and baking to prepare the porous layer powder. The porous layer powder is mixed with a binder, a dispersant and an organic solvent and ball milled to obtain a porous layer impregnated slurry. Dip-coating the porous layer impregnating slurry on the surface of the porous ceramic support to be deposited, and drying.

Wherein, alcohol may be used as the ball milling medium during the ball milling process of mixing the second ceramic powder and the pore-forming agent, and the ball milling time may be 12-24 hours. The slurry obtained after ball milling the second ceramic powder and the pore-forming agent is baked to obtain the porous layer powder.

Subsequently, the porous layer powder, the binder and the dispersant are added to the ball mill tank, the organic solvent is added to the preset slurry solid content (such as 5-20wt%, preferably 5-10wt%), and the grinding is carried out for 24-72h, A light gray porous layer impregnation slurry can be obtained.

Subsequently, the impregnated slurry for the porous layer is uniformly deposited on the surface of the porous ceramic support body to be deposited by using a dip coating method. Dip coating times can be 3-5 times. The drying temperature after dip coating can be 30-50°C.

Further, an electrolyte layer is deposited on the surface of the porous layer to be deposited.

For reference, the preparation of the electrolyte layer may include: ball milling and baking the second ceramic powder in the preparation raw materials of the electrolyte layer to obtain the electrolyte layer powder. The electrolyte layer powder is mixed with a binder, a dispersant and an organic solvent and ball-milled to obtain an electrolyte layer impregnated slurry. The electrolyte layer impregnating slurry is impregnated and coated on the surface of the porous layer to be deposited, and dried.

Wherein, absolute ethanol may be used as a ball milling medium during the ball milling process of the second ceramic powder, and the ball milling time may be 12-24 hours. The powder of the electrolyte layer can be obtained by baking the ball-milled slurry.

Subsequently, the electrolyte layer powder, binder and dispersant are added to the ball mill tank, and the organic solvent is added to reach the preset slurry solid content (such as 10-20wt%), and ground for 24-72 hours to obtain a white electrolyte impregnated slurry.

Subsequently, the electrolyte impregnation slurry is uniformly deposited on the surface of the porous layer to be deposited by a dip coating method. The number of times of dip coating in this process can also be 3-5 times. The drying temperature after dip coating can be 30-50°C.

Further, a porous electrode is deposited on the surface to be deposited of the electrolyte layer.

When the porous electrode is a porous anode, the preparation of the porous anode may include: mixing and grinding the anode powder, pore former and binder solution in the preparation raw materials of the porous anode to obtain an anode slurry (green). An anode slurry is deposited on the surface to be deposited of the electrolyte layer.

Wherein, the anode powder nickel oxide can be obtained by calcining dinickel trioxide at 750-850°C (eg 800°C) for 1.5-2.5h (eg 2h).

The grinding time of the anode powder, the pore former and the binder solution in the mortar can be 3-4 hours.

When the porous electrode is a porous cathode, the preparation of the porous cathode includes: mixing and grinding the cathode powder, pore forming agent and binder solution in the preparation raw materials of the porous cathode to obtain cathode slurry (gray). The cathode slurry is deposited on the surface to be deposited of the electrolyte layer.

Among them, the cathode powder (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ powder can be obtained in the following manner: calcining dilanthanum trioxide at 950-1050°C (such as 1000°C) for 3.5-4.5h (such as 4h ), dry strontium carbonate at 115-125°C (such as 120°C), dry manganese carbonate at 115-125°C (such as 120°C), and then add the above three into the ball mill tank in sequence according to stoichiometric Dehydrated ethanol is used as the ball milling medium, triethanolamine is used as the dispersant, ball milled at a speed of 380-420r/min (such as 400r/min) for 0.8-1.2h (such as 1h), after filtration, the ) drying, and then calcined at 1000-1100°C (eg 1050°C) for 3.5-4.5h (eg 4h).

The grinding time of the cathode powder, the pore forming agent and the binder solution in the mortar can also be 3-4 hours.

Further, the anode slurry or the cathode slurry is uniformly deposited on the surface of the electrolyte layer to be deposited by using a screen printing method.

For reference, the screen printing times may be 1-2 times. After printing, dry it at 30-50°C to get the cell skeleton blank.

Further, after the cell skeleton green body is completely dried, it is calcined at a high temperature. For details, please refer to: put the battery skeleton blank into a high-temperature furnace, and heat it at 1-5°C/min (such as 1°C/min, 2°C/min, 3°C/min, 4°C/min or 5°C/min, etc.) The heating rate is raised to 1300-1400°C in stages (such as 1300°C, 1320°C, 1350°C, 1380°C or 1400°C, etc.), and then kept for 5-10h, and then at 3-5°C/min (such as 3°C/min , 3.5°C/min, 4°C/min, 4.5°C/min or 5°C/min, etc.) to cool down to room temperature in stages to obtain a battery skeleton.

Further, the porous ceramic support and the porous layer are impregnated with an electrode material opposite in polarity to the porous electrode, followed by calcination.

In an optional embodiment, the total impregnation of the electrode material is 10-20 wt%, such as 10 wt%, 15 wt% or 20 wt%, of the entire electrode-supported solid oxide fuel cell.

The impregnation solution can be prepared by citric acid complexation method, and the metal ion concentration in the impregnation solution is 0.5-1mol/L, such as 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L etc.

In an optional embodiment, the impregnation process is to use the ion impregnation method for multiple impregnations, and after each impregnation except the last impregnation, it is calcined at 400-500°C (preferably 450°C) for 0.5-1.5h (preferably 1h) , calcining at 800-900°C (preferably 850°C) for 1.5-2.5h (preferably 2h) after the last impregnation.

In an optional embodiment, after the last impregnation, the temperature is raised to 280-320°C at a rate of 2.5-3.5°C/min, and then to 800-900°C at a rate of 1.5-2.5°C/min before calcination.

The characteristics and performance of the present invention will be described in further detail below in conjunction with the examples.

Example 1

This embodiment provides an electrode-supported solid oxide fuel cell, the preparation process of which is as follows:

(1) Preparation of 3YSZ porous ceramic support 1 (thickness 700 μm)

Add 3mol% YSZ ceramic powder and 5wt% pore-forming agent (graphite: PMMA=3:7, mass ratio) to the ball mill pot, add absolute ethanol as the ball mill medium, and ball mill for 12 hours to obtain a slurry. Dry at 80°C to obtain 3YSZ-pore-forming agent mixed powder. Among them, the particle diameter of the ceramic powder is 0.5 μm, and the specific surface area is 10 m ² /g.

An organic solution prepared by combining binder polyethersulfone (PESf), dispersant polyvinylpyrrolidone (PVP) and organic solvent 1-2-methylpyrrolidone (NMP) in a weight ratio of 4:1:20. Put the 3YSZ-pore forming agent mixed powder into a ball mill tank, and add an organic solution at a weight ratio of 1:1.5, then add an appropriate amount of ball mill beads and mill for 24 hours to obtain a polymer slurry, which is vacuum degassed for 30 minutes. Adjust the blade height of the casting scraper to 1 mm, pour the defoamed polymer slurry, and cast to obtain a green body with a thickness of 1 mm. Immediately immerse the green body in water for phase inversion, remove after soaking for 12 hours, dry in an oven at 80°C, cut into discs with a diameter of 20mm, and place it in a high-temperature furnace for calcination at 1100°C for 2 hours to obtain a 3YSZ porous ceramic support 1.

Calcination procedure: room temperature → (3°C/min) 300°C → (1°C/min) 850°C, 4h → (2°C/min) 1100°C, 2h → (2°C/min) 400°C → natural cooling.

(2) Preparation of porous layer 2 (thickness is 20 μm)

Calcining SSZ ceramic powder at 1000°C to obtain SSZ-1000 powder, adding SSZ powder, SSZ-1000 powder and pore-forming agent (graphite: PMMA = 3:7, mass ratio) at a mass ratio of 2:8:0.5 In a ball milling tank, use alcohol as a ball milling medium, mill for 12 hours to obtain a slurry, and dry a porous layer powder at 80°C.

Add the porous layer powder, the organic solvent terpineol, the binder ethylcellulose solution and the dispersant triethanolamine in a weight ratio of 4:34.9:1:0.1 into a ball mill jar, and mill for 36 hours to form a porous layer slurry. The porous layer slurry was evenly deposited on the surface of the porous ceramic support 1 to be deposited by a dipping coating method, the number of dipping coatings was 3 times, and the slurry was placed in an oven at 40° C. for drying.

(3) Preparation of dense electrolyte layer 3 (15 μm in thickness)

Calcining SSZ ceramic powder at 1000°C to obtain SSZ-1000 powder, adding SSZ powder and SSZ-1000 powder into a ball milling tank at a weight ratio of 2:8, using absolute ethanol as a ball milling medium, and ball milling for 12 hours to obtain a slurry The material was dried at 80°C to obtain the electrolyte layer powder. The electrolyte layer powder, the solvent terpineol, the binder ethylcellulose solution and the dispersant triethanolamine were added into the ball mill tank at a weight ratio of 4:34.9:1:0.1, and ball milled for 36 hours to obtain the electrolyte layer slurry. The electrolyte layer slurry was evenly deposited on the surface of the porous layer 2 to be deposited by dip coating method, the number of dip coating was 3 times, and placed in an oven for drying at 40°C.

(4) Preparation of porous electrode 4 (porous anode, thickness 20 μm)

Ni ₂ O ₃ was calcined at 800°C for 2 hours to obtain NiO powder, and the weight ratio of NiO powder, SSZ powder, SSZ-1000 powder and pore-forming agent (graphite: PMMA=3:7) was 20:4:16 : 1 Mix evenly to obtain anode powder. The anode powder and the binder ethylcellulose solution were added into a mortar at a weight ratio of 1:1 and ground for 3.5 hours to obtain an anode slurry. The anode slurry was uniformly deposited on the surface of the electrolyte layer 3 to be deposited by screen printing method, the number of screen printing was 1, and the battery skeleton was dried at 40° C. to obtain a cell skeleton green body.

After the battery skeleton green body is completely dried, it is placed in a high-temperature furnace for calcination. The calcination procedure is: room temperature → (2/min) 200°C → (1.5°C/min) 600°C, 2h → (2°C/min) 800°C, 2h →(1.5°C/min) 1350°C, 5h→(2°C/min) 1000°C, 2h→(2°C/min) 400°C→naturally cool down, take it out after cooling down, polish off the side of the sponge layer of the support, make the fingers The holes are exposed to obtain a battery skeleton.

(5) Preparation and screening of impregnated cathode materials

La _0.8 Sr _0.2 Co _0.5 Fe _0.5 O _3-δ (LSCF) and (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ (LSM95) impregnation solutions with a metal ion concentration of 1mol/L were prepared by citric acid complexation. A kind of impregnating solution is impregnated on the symmetric cell, and the electrochemical impedance spectrum test is carried out, and the cathode material is determined according to the impedance spectrum. The total amount of impregnation is 10wt%, 15wt%, 20wt%; the final calcination temperature is 800°C, 850°C; the test atmosphere is Air, O ₂ ; the test temperature is 650-850°C. According to the impedance spectrum, the polarization impedance of LSCF calcined at 800℃ was the smallest in O ₂ atmosphere, and the polarization impedance showed a downward trend with the increase of impregnation amount. Therefore, it is finally determined that the cathode impregnation material is LSCF, and the cathode raw gas is O ₂ .

(6) Impregnated cathode

Immerse the screened cathode material in the porous support and porous layer 2 of the battery skeleton, the total amount of impregnation is 15wt%, and dry at 450°C for 1h after each impregnation, and calcinate the last impregnated battery at 850°C for 2h to obtain a complete Battery.

Calcination procedure: room temperature → (3°C/min) 300°C → (2°C/min) 850°C-2h → natural cooling.

Example 2

This embodiment provides an electrode-supported solid oxide fuel cell, the preparation process of which is as follows:

(1) Preparation of 4YSZ porous ceramic support (thickness 600 μm)

Add 4mol% YSZ ceramic powder and 10wt% pore-forming agent (spherical carbon powder: PMMA=3:7, mass ratio) into the ball milling tank, add absolute ethanol as the ball milling medium, and ball mill for 12 hours to obtain slurry The material was dried at 80°C to obtain 4YSZ-pore-forming agent mixed powder. Among them, the particle size of the ceramic powder is 0.1 μm, and the specific surface area is 15 m ² /g.

An organic solution prepared by combining binder polyethersulfone (PESf), dispersant polyvinylpyrrolidone (PVP) and organic solvent 1-2-methylpyrrolidone (NMP) in a weight ratio of 3:0.5:18. Put the 4YSZ-pore forming agent mixed powder into a ball mill tank, and add an organic solution at a weight ratio of 1:1, then add an appropriate amount of ball mill beads and mill for 12 hours to obtain a polymer slurry, which is vacuum degassed for 30 minutes. Adjust the blade height of the casting scraper to 1 mm, pour the defoamed polymer slurry, and cast to obtain a green body with a thickness of 0.7 mm. Immediately immerse the green body in water for phase inversion, remove after soaking for 12 hours, dry in an oven at 40°C, cut into discs with a diameter of 15mm, and place it in a high-temperature furnace for calcination at 1100°C for 2 hours to obtain a 3YSZ porous ceramic support.

Calcination procedure: room temperature → (1°C/min) 800°C, 3h → (3°C/min) room temperature.

(2) Preparation of porous layer

Calcining SSZ ceramic powder at 950°C to obtain SSZ-950 powder, the mass ratio of SSZ powder, SSZ-950 powder and pore-forming agent (spherical carbon powder: PMMA=3:7, mass ratio) is 2.5:7.5: 0.8 was added to a ball mill jar, and alcohol was used as a ball mill medium for 18 hours of ball milling to obtain a slurry, which was dried at 80°C as a porous layer powder.

Add the porous layer powder, the organic solvent terpineol, the binder ethylcellulose solution and the dispersant triethanolamine into the ball mill tank at a weight ratio of 4:34.9:0.8:0.08, and ball mill for 24 hours to form a porous layer slurry. The slurry of the porous layer was uniformly deposited on the porous ceramic support by dip coating method, the number of dip coating was 4 times, and it was dried in an oven at 30°C.

(3) Preparation of dense electrolyte layer

Calcining SSZ ceramic powder at 950°C to obtain SSZ-950 powder, adding SSZ powder and SSZ-950 powder to a ball mill pot at a weight ratio of 2.5:7.5, using absolute ethanol as a ball mill medium, and ball milling for 18 hours to obtain a slurry The material was dried at 80°C to obtain the electrolyte layer powder. The electrolyte layer powder, the solvent terpineol, the binder ethylcellulose solution and the dispersant triethanolamine were added into the ball mill tank at a weight ratio of 4:34.9:0.8:0.08, and ball milled for 24 hours to obtain the electrolyte layer slurry. The electrolyte layer slurry was uniformly deposited on the surface of the porous layer to be deposited by a dip coating method, and the number of dip coating was 4 times, and placed in an oven for drying at 40°C.

(4) Porous anode preparation

Ni ₂ O ₃ was calcined at 750°C for 2.5h to obtain NiO powder, and the NiO powder, SSZ powder, SSZ-950 powder and pore-forming agent (spherical carbon powder: PMMA=3:7, mass ratio) were calculated by weight The ratio of 18:3:15:0.8 is mixed uniformly to obtain anode powder. The anode powder and the binder ethylcellulose solution were added into a mortar at a weight ratio of 1:0.8 and ground for 3 hours to obtain an anode slurry. The anode slurry was uniformly deposited on the surface of the electrolyte layer to be deposited by the screen printing method, and the number of screen printing was 1 time, and dried at 30°C to obtain the battery skeleton blank.

After the battery skeleton green body is completely dried, it is placed in a high-temperature furnace for calcination. The calcination procedure is: room temperature → (1/min) 1300°C, 5h → (3°C/min) room temperature, take it out after cooling down, and polish off the side of the support sponge layer , so that the finger holes are exposed to obtain the battery skeleton.

(5) impregnated cathode

Impregnate the screened cathode material (cathode impregnation material is LSCF, cathode raw material gas is O ₂ ) in the porous support and porous layer of the battery skeleton, the total amount of impregnation is 10wt%, and dried at 400°C for 1.5h after each impregnation , the battery impregnated for the last time was calcined at 800°C for 2.5h to obtain a full battery.

Calcination procedure: room temperature → (3°C/min) 300°C → (2°C/min) 800°C, 2.5h → natural cooling.

Example 3

This embodiment provides an electrode-supported solid oxide fuel cell, the preparation process of which is as follows:

(1) Preparation of 5SZ porous ceramic support (thickness 800 μm)

Add 5mol% YSZ ceramic powder and 15wt% pore-forming agent (soluble starch: PMMA=3:7, mass ratio) into the ball milling tank, add absolute ethanol as the ball milling medium, and ball mill for 12 hours to obtain a slurry , and dried at 80°C to obtain 5YSZ-pore-forming agent mixed powder. Among them, the particle size of the ceramic powder is 1 μm, and the specific surface area is 8 m ² /g.

An organic solution prepared by combining binder polyethersulfone (PESf), dispersant polyvinylpyrrolidone (PVP) and organic solvent 1-2-methylpyrrolidone (NMP) in a weight ratio of 5:1.5:22. Put the 5YSZ-pore-forming agent mixed powder into a ball mill tank, and add an organic solution at a weight ratio of 1:2, then add an appropriate amount of ball mill beads and mill for 18 hours to obtain a polymer slurry, which is vacuum degassed for 30 minutes. Adjust the blade height of the casting scraper to 1 mm, pour the defoamed polymer slurry, and cast to obtain a green body with a thickness of 1.2 mm. Immediately immerse the green body in water for phase inversion, remove after soaking for 12 hours, dry in an oven at 50°C, cut into discs with a diameter of 25mm, and place them in a high-temperature furnace for calcination at 1100°C for 2 hours to obtain a 3YSZ porous ceramic support.

Calcination procedure: room temperature → (5°C/min) 1200°C, 1h → (5°C/min) room temperature.

(2) Preparation of porous layer

The SSZ ceramic powder is calcined at 1100°C to obtain SSZ-1100 powder, and the mass ratio of SSZ powder, SSZ-1100 powder and pore-forming agent (soluble starch: PMMA=3:7, mass ratio) is 3:7:1 Put it into a ball mill jar, use alcohol as a ball mill medium, and mill for 24 hours to obtain a slurry, which is then dried at 80° C. as a porous layer powder.

Add the porous layer powder, the organic solvent terpineol, the binder ethylcellulose solution and the dispersant triethanolamine into the ball mill tank at a weight ratio of 4:34.9:1.2:0.12, and ball mill for 72 hours to form a porous layer slurry. The slurry of the porous layer was uniformly deposited on the porous ceramic support by a dipping coating method, the number of dipping coatings was 5 times, and the slurry was placed in an oven at 50° C. for drying.

(3) Preparation of dense electrolyte layer

Calcining SSZ ceramic powder at 1100°C to obtain SSZ-1100 powder, adding SSZ powder and SSZ-1100 powder to the ball milling tank at a weight ratio of 3:7, using absolute ethanol as the ball milling medium, ball milling for 24 hours to obtain slurry The material was dried at 80°C to obtain the electrolyte layer powder. The electrolyte layer powder, the solvent terpineol, the binder ethylcellulose solution and the dispersant triethanolamine were added into the ball mill tank at a weight ratio of 4:34.9:1.2:0.12, and ball milled for 72 hours to obtain the electrolyte layer slurry. The electrolyte layer slurry was evenly deposited on the surface of the porous layer to be deposited by a dipping coating method, the number of dipping coatings was 5 times, and it was placed in an oven for drying at 40°C.

(4) Porous anode preparation

Ni ₂ O ₃ was calcined at 850°C for 1.5h to obtain NiO powder. The NiO powder, SSZ powder, SSZ-1100 powder and pore-forming agent (soluble starch: PMMA=3:7, mass ratio) were calculated as 22:5:17:1.2 Mix evenly to obtain anode powder. The anode powder and the binder ethylcellulose solution were added into a mortar at a weight ratio of 1:0.9 and ground for 4 hours to obtain an anode slurry. The anode slurry was uniformly deposited on the surface of the electrolyte layer to be deposited by screen printing method, the number of screen printing was 2 times, and it was dried at 50°C to obtain the battery skeleton blank.

After the battery skeleton green body is completely dried, it is placed in a high-temperature furnace for calcination. The calcination procedure is: room temperature → (5/min) 1400°C, 10h → (5°C/min) room temperature, take it out after cooling down, and polish off the side of the sponge layer of the support , so that the finger holes are exposed to obtain the battery skeleton.

(5) impregnated cathode

Impregnate the screened cathode material (cathode impregnation material is LSCF, cathode raw material gas is O ₂ ) in the porous support and porous layer of the battery skeleton, the total amount of impregnation is 20wt%, and after each impregnation, dry at 500°C for 0.5h , the battery impregnated for the last time was calcined at 900°C for 1.5h to obtain a full battery.

Calcination procedure: room temperature → (3°C/min), 300°C → (2°C/min), 900°C, 1.5h → natural cooling.

Example 4

The difference between this embodiment and embodiment 1 is:

Porous electrodes are porous cathodes prepared by:

Calcinate dilanthanum trioxide (La ₂ O ₃ ) at 1000°C for 4 hours, dry strontium carbonate (SrCO ₃ ) at 120°C, dry manganese carbonate (MnCO ₃ ) at 120°C, and add them to the ball mill tank in sequence according to the preset stoichiometric ratio , using absolute ethanol as the ball milling medium and triethanolamine (TEA) as the dispersant, ball milling at 400r/min for 1h, filtered and dried at 80°C, calcined at 950°C for 4h after drying, and then ball milled with an appropriate amount of absolute ethanol as the ball milling medium After filtering for 1 hour, dry at 80°C and calcinate at 1050°C for 4 hours to obtain (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ (LSM95) powder. Weigh LSM95 powder, SSZ powder, SSZ-1000 powder and pore-forming agent in a weight ratio of 20:4:16:1, and mix them uniformly to obtain cathode powder. Put the cathode powder and the binder solution into a mortar at a mass ratio of 1:1 and grind for 4 hours to obtain cathode slurry. The cathode slurry was evenly deposited on the surface of the electrolyte layer to be deposited by the screen printing method, and the number of screen printing was 1 time, and dried at 40°C to obtain the battery skeleton blank.

After the battery skeleton green body is completely dried, it is placed in a high-temperature furnace for calcination. The calcination procedure is: room temperature → (2/min) 200°C → (1.5°C/min) 600°C, 2h → (2°C/min) 800°C, 2h →(1.5°C/min) 1350°C, 5h→(2°C/min) 1000°C, 2h→(2°C/min) 400°C→naturally cool down, take it out after cooling down, polish off the side of the sponge layer of the support, make the fingers The holes are exposed to obtain a battery skeleton.

The impregnated material is an impregnated anode material, and the screened anode material (SrFe _0.75 Mo _0.25 O _3-δ ) is impregnated in the porous support and porous layer of the battery skeleton, the total amount of impregnation is 15wt%, and baked at 450°C after each impregnation. After drying for 1 hour, the impregnated battery was calcined at 850°C for 2 hours to obtain a full battery.

Test case

The structure of the electrode-supported solid oxide fuel cell prepared in Example 1 was observed, and the results are shown in Figures 1-4. From Figures 1-4 of the scanning electron microscope, it can be seen that each of the cathode-supported SOFCs prepared in this example The layers are closely bonded without cracking or delamination; the impregnating liquid is evenly distributed; the overall flatness of the battery is good.

In addition, the flexural strength of the 3YSZ porous ceramic support in the electrode-supported solid oxide fuel cell prepared in Example 1 was measured by the three-point bending method, and the flexural strength formula is: σf=3FL/2BH ² . Among them, F represents the force at break; B represents the width of the sample; H represents the height of the sample; L represents the length of the sample, and the results are shown in Table 1:

Table 1 Determination results of flexural strength

It can be seen from Table 1 that the average flexural strength of the 3YSZ porous ceramic support in Example 1 can reach 131.95MPa, and the flexural performance is excellent, which can effectively solve the problem of cracking and fracture of the battery during the test process.

In summary, this application replaces the method used in the prior art by using the Y ₂ O ₃ -ZrO ₂ mixture containing 3-5 mol% Y ₂ O ₃ as the main raw material for the preparation of porous ceramic supports and combining impregnated electrodes. _The method for preparing the support body skeleton from the _{Y2O3 - ZrO2} mixture of the electronically conductive phase and 8mol% _Y2O3 can effectively improve the overall fracture strength of the support body prepared by the phase inversion method and the fuel cell containing the above support body . The preparation method of the fuel cell is simple and easy to operate, and is suitable for industrial production.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (31)

1. An electrode-supported solid oxide fuel cell, characterized in that it comprises a porous ceramic support prepared by a phase inversion method; the raw material for preparing the porous ceramic support comprises a first ceramic powder, and the first The ceramic powder is a Y ₂ O ₃ -ZrO ₂ mixture containing 3-5mol% Y ₂ O ₃ ; The porous ceramic support is impregnated with electrode material; The thickness of the porous ceramic support is 600-800 μm; The particle size of the first ceramic powder is 0.1-1 μm; The specific surface area of the first ceramic powder is 8-15m ² /g; The electrode-supported solid oxide fuel cell further includes a porous layer for depositing on one surface of the porous ceramic support in the thickness direction; The thickness of the porous layer is 25-35 μm; The overall porosity of the porous ceramic support and the porous layer is 25-35%; The raw material for preparing the porous layer includes a second ceramic powder, the second ceramic powder includes a first scandia-stabilized zirconia and a second scandia-stabilized zirconia, and the second scandia-stabilized zirconia Obtained by calcining zirconia stabilized by the first scandium oxide at 950-1100°C for 1.5-2.5 hours; In the second ceramic powder, the mass ratio of the first scandia-stabilized zirconia to the second scandia-stabilized zirconia is 2:8-3:7. 2. The electrode-supported solid oxide fuel cell according to claim 1, wherein the raw materials for the preparation of the porous ceramic support body also include a pore-forming agent; the amount of the pore-forming agent added is 5-15wt% of the raw material for the preparation of the support. 3. The electrode-supported solid oxide fuel cell according to claim 2, characterized in that, in the raw materials for the preparation of the porous ceramic support, the amount of the pore-forming agent added is the amount of the preparation of the porous ceramic support. 5-10wt% of the raw material. 4. The electrode-supported solid oxide fuel cell according to claim 1, characterized in that the raw material for the preparation of the porous ceramic support body also includes viscose with a mass ratio of 3-5:0.5-1.5:18-22. Additives for binders, dispersants and organic solvents. 5. The electrode-supported solid oxide fuel cell according to claim 4, characterized in that, among the raw materials for the preparation of the porous ceramic support, the total mass of the first ceramic powder and pore-forming agent is the same as that of the The mass ratio of additives is 1:1-3. 6. The electrode-supported solid oxide fuel cell according to claim 5, characterized in that, among the raw materials for the preparation of the porous ceramic support, the total mass of the first ceramic powder and the pore-forming agent is equal to The mass ratio of the additives is 1:1.5-2. 7. The electrode-supported solid oxide fuel cell according to claim 1, wherein the raw materials for the preparation of the porous layer also include pore-forming agents and additives containing binders, dispersants and organic solvents; In the raw materials for the preparation of the porous layer, the amount of the pore-forming agent added is 5-10wt% of the second ceramic powder; the total mass of the second ceramic powder and the pore-forming agent is the same as the The mass ratio of the binder and the dispersant is 100:20-30:2-3. 8. The electrode-supported solid oxide fuel cell according to claim 1, characterized in that, the electrode-supported solid oxide fuel cell further comprises an electrolyte layer, and the electrolyte layer is used for depositing on the porous layer the surface of the side away from the porous ceramic support; The thickness of the electrolyte layer is 10-20 μm; The raw materials for the preparation of the electrolyte layer include the second ceramic powder and additives containing a binder, a dispersant and an organic solvent; The mass ratio of the second ceramic powder used in the preparation raw materials of the electrolyte layer to the binder and the dispersant is 100:20-30:2-3. 9. The electrode-supported solid oxide fuel cell according to claim 8, characterized in that, the electrode-supported solid oxide fuel cell further comprises a porous electrode, and the porous electrode is used for depositing on the electrolyte layer the surface of the side facing away from the porous layer; The thickness of the porous electrode is 25-35 μm. 10. The electrode-supported solid oxide fuel cell according to claim 9, wherein when the porous electrode is a porous anode, the raw materials for preparing the porous anode include anode powder and a pore-forming agent; The anode powder includes nickel oxide and the second ceramic powder; In the raw materials for preparing the porous anode, the mass ratio of the nickel oxide, the first scandia-stabilized zirconia to the second scandia-stabilized zirconia and the pore-forming agent is 18-22:3 -5:15-17:0.8-1.2; The raw material for preparing the porous anode also includes a binder solution, and the mass ratio of the binder solution to the anode powder is 80-100:100. 11. The electrode-supported solid oxide fuel cell according to claim 10, wherein when the porous electrode is a porous cathode, the raw materials for preparing the porous cathode include cathode powder and a pore-forming agent; The cathode powder includes (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ powder and the second ceramic powder; Among the raw materials for preparing the porous cathode, the (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ powder, the first scandia-stabilized zirconia and the second scandia-stabilized zirconia and the The mass ratio of the pore agent is 18-22:3-5:15-17:0.8-1.2; The raw materials for preparing the porous cathode further include a binder solution, and the mass ratio of the binder solution to the cathode powder is 80-100:100. 12 . The electrode-supported solid oxide fuel cell according to claim 11 , wherein the binder solution in the raw materials for the preparation of the porous anode and the porous cathode is an ethyl cellulose solution. 13 . 13. The electrode-supported solid oxide fuel cell according to claim 11, characterized in that the porous ceramic support, the porous layer, and the porous electrode used in the pore-forming agent all include soluble starch, graphite , at least one of spherical carbon powder and polymethyl methacrylate microspheres. 14. The electrode-supported solid oxide fuel cell according to claim 13, wherein the pore-forming agents used in the porous ceramic support, the porous layer, and the porous electrode all include graphite and polyformaldehyde At least one of methyl acrylate microspheres. 15 . The electrode-supported solid oxide fuel cell according to claim 11 , wherein both the porous ceramic support and the porous layer are impregnated with an electrode material having a polarity opposite to that of the porous electrode. 16. The electrode-supported solid oxide fuel cell according to claim 15, wherein when the porous electrode is an anode electrode, the electrode material used for impregnation includes La _0.8 Sr _0.2 Co _0.5 Fe _0.5 O At least one of _3-δ and (La _0.8 Sr _0.2 ) _0.95 MnO _3-δ , when the porous electrode is a cathode electrode, the electrode material used for impregnation includes SrFe _0.75 Mo _0.25 O _3-δ , La At least one of _1-x Sr _x Ni _0.4 Fe _0.6 O _3-δ or La _1-x Sr _x Ni _0.6 Fe _0.4 O _3-δ ; Wherein, x in La _1-x Sr _x Ni _0.4 Fe _0.6 O _3-δ and La _1-x Sr _x Ni _0.6 Fe _0.4 O _3-δ takes any value greater than 0 and less than 1. 17. The method for preparing an electrode-supported solid oxide fuel cell according to any one of claims 1-16, characterized in that it comprises the following steps: preparing the raw material for the porous ceramic support by a phase inversion method The porous ceramic support. 18. The preparation method according to claim 17, characterized in that, the preparation of the porous ceramic support comprises: the first ceramic powder, pore-forming agent and The mixture of additives is ball milled and cast to obtain a green body; the green body is phase-inverted in a non-solvent, completely cured and then dried; followed by sintering and discharging the binder and pore-forming agent; The thickness of the green body is 0.7-1.2mm; Described non-solvent is deionized water; The phase inversion time is 12-24h; The sintering process is to raise the temperature to 800-1200°C at a heating rate of 1-5°C/min, keep the temperature for 1-3h, and then lower the temperature to 10-35°C at a cooling rate of 3-5°C/min. 19. The preparation method according to claim 18, further comprising: depositing a porous layer on one surface of the porous ceramic support in the thickness direction. 20. The preparation method according to claim 19, characterized in that, the preparation of the porous layer comprises: mixing the second ceramic powder in the raw materials for the preparation of the porous layer with a pore-forming agent, followed by ball milling and baking , making a porous layer powder; mixing the porous layer powder with a binder, a dispersant and an organic solvent and ball milling to obtain a porous layer impregnating slurry; dipping and coating the porous layer impregnating slurry on the The surface to be deposited on the porous ceramic support is dried; The ball milling time of the second ceramic powder and the pore-forming agent is 12-24 hours; the ball milling time of the porous layer powder and the binder, the dispersant and the solvent is 24-72 hours; The solid content of the slurry after the porous layer powder is mixed with the binder, the dispersant and the organic solvent is 5-20wt%. 21. The preparation method according to claim 20, characterized in that the solid content of the slurry mixed with the porous layer powder, the binder, the dispersant and the organic solvent is 5-10wt %. 22. The preparation method according to claim 20, further comprising: depositing an electrolyte layer on the surface of the porous layer to be deposited. 23. The preparation method according to claim 22, characterized in that the preparation of the electrolyte layer comprises: ball milling and baking the second ceramic powder in the preparation raw materials of the electrolyte layer to obtain the electrolyte layer powder body; the electrolyte layer powder is mixed with a binder, a dispersant and an organic solvent and ball milled to obtain an electrolyte layer impregnation slurry; the electrolyte layer impregnation slurry is impregnated and coated on the surface to be deposited of the porous layer ,drying; The ball milling time of the second ceramic powder is 12-24h; the ball milling time of the electrolyte layer powder and the binder, the dispersant and the solvent is 24-72h; The solid content of the slurry after mixing the electrolyte layer powder, the binder, the dispersant and the organic solvent is 10-20wt%. 24. The preparation method according to claim 23, further comprising: depositing a porous electrode on the surface to be deposited of the electrolyte layer. 25. The preparation method according to claim 24, characterized in that, when the porous electrode is a porous anode, the preparation of the porous anode comprises: anode powder, pore-forming mixing and grinding the agent and the binder solution to obtain an anode slurry; depositing the anode slurry on the surface to be deposited of the electrolyte layer. 26. The preparation method according to claim 25, characterized in that, when the porous electrode is a porous cathode, the preparation of the porous cathode comprises: the cathode powder in the preparation raw materials of the porous cathode, the pore-forming mixing and grinding the agent and the binder solution to obtain cathode slurry; depositing the cathode slurry on the surface to be deposited of the electrolyte layer. 27. The preparation method according to claim 26, characterized in that, the anode slurry and the cathode slurry are deposited by screen printing. 28. The preparation method according to claim 26, characterized in that the porous ceramic support and the porous layer are jointly impregnated with an electrode material opposite in polarity to the porous electrode, followed by calcination. 29. The preparation method according to claim 28, characterized in that the total amount of impregnation of the electrode material is 10-20wt% of the entire electrode-supported solid oxide fuel cell. 30. The preparation method according to claim 29, characterized in that the ion impregnation method is used for multiple impregnations, and after each impregnation except the last impregnation, it is calcined at 400-500°C for 0.5-1.5h, and the last impregnation Then calcined at 800-900°C for 1.5-2.5h. 31. The preparation method according to claim 30, characterized in that after the last immersion, the temperature is raised to 280-320°C at a rate of 2.5-3.5°C/min, and then heated to 280-320°C at a rate of 1.5-2.5°C/min Calcination is carried out after 800-900°C.

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