CN112768704B - Proton conduction type electrolyte-based solid oxide fuel cell and preparation method thereof - Google Patents
Proton conduction type electrolyte-based solid oxide fuel cell and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8867—Vapour deposition
- H01M4/8871—Sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a solid oxide fuel cell based on proton conduction electrolyte and a preparation method thereof, wherein the electrolyte material in the traditional SOFC single cell is CD 1‑x M x O 3‑δ Proton conducting electrolyte material with perovskite structure is used for replacing and matched AA' B 2 O 6‑δ The cathode material of the double-layer perovskite structure is characterized in that an anode layer and a cathode layer of the SOFC single cell are prepared by magnetron sputtering by adopting a metal oxide target material containing a pore-forming agent, and an electrolyte layer is prepared by magnetron sputtering by adopting a metal oxide target material without a pore-forming agent. The method has the advantages of wide material selection, simple preparation process, no use of organic solvents, binders, plasticizers, activators, other organic assistants and the like in the whole process, and belongs to an environment-friendly processing preparation means and process.
Description
Technical Field
The invention belongs to the technical field of Solid Oxide Fuel Cells (SOFC), and particularly relates to a solid oxide fuel cell based on proton conduction electrolyte and a preparation method thereof.
Background
The conventional SOFC single cell uses an oxygen ion conductive electrolyte, so that the electrochemical reaction of the cathode part dominates the reaction of the whole cell, but the catalytic activity and the ionic conductivity of the LSM (strontium doped lanthanum manganate) and LSCF (strontium doped lanthanum iron cobaltate) materials used in the conventional SOFC single cell are relatively low, so that the performance of the whole cell is greatly affected.
The traditional SOFC single cell based on the oxygen ion conduction electrolyte has the defects of high working temperature (650-850 ℃), large internal impedance, easiness in carbon deposition and the like, so that the application scene is limited, and the reliability and the service life of the SOFC single cell are greatly influenced. Later researchers developed a solid oxide fuel cell based on proton conducting electrolyte materials, with the proton conducting electrolyte conducting medium being protons, i.e., hydrogen ions. In the working process of the fuel cell taking the proton conductor material as the electrolyte, the fuel gas is dissociated into protons and electrons after being catalyzed by the anode, the protons and the electrons respectively reach the cathode through the proton conduction type electrolyte and an external circuit, and the protons react with oxygen ions at one side of the cathode to generate water, so that external power supply is realized. The electrochemical reaction of the anode part of the proton conduction electrolyte material dominates the electrochemical reaction of the whole battery, so that the problem of low catalytic activity of the cathode material to oxygen can be effectively overcome, and the reaction temperature is reduced.
However, no matter what conductive type electrolyte material is used for the SOFC device, the conventional preparation process is based on the traditional process of ceramic casting and screen printing, and a large amount of organic auxiliary agents are used in the process, so that the environment and the health of experimental staff are seriously influenced.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, adopts a novel proton conduction type electrolyte material and designs a novel device structure based on the novel proton conduction type electrolyte material.
The invention further aims to provide a preparation method of the proton conduction type electrolyte-based solid oxide fuel cell, wherein the whole preparation process adopts magnetron sputtering without introducing organic auxiliary agents to prepare a single cell device, and the whole process is short in time consumption and easy to operate.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a solid oxide fuel cell based on proton conducting electrolyte comprises a nickel oxide NiO porous anode layer, a dense electrolyte layer and a porous cathode layer, wherein the cathode layer comprises AA' B with a double-layer perovskite structure 2 O 6-δ Crystalline material wherein A is any of the lanthanide La series rare earth elementsOne or two of A' is barium Ba, B is any one or two of transition metal elements in the fourth period;
the electrolyte layer comprises a structure of CD 1-x M x O 3-δ A proton conducting electrolyte material of a perovskite structure, wherein C is any one or two of divalent alkaline earth metal elements, D is any one or two of tetravalent transition metal elements or rare earth metal elements, M is any one or two of trivalent transition metal elements or rare earth metal elements, wherein x represents the number of doping atoms M occupying the D position in a single unit cell, between 0 and 1; delta represents the number of oxygen defects in a single unit cell.
In a specific embodiment, the cathode layer AA' B 2 O 6-δ The A in the crystal material is selected from one or two of La, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu; b is selected from scandium Sc, titanium Ti, chromium Cr, manganese Mn, iron Fe, cobalt Co, nickel Ni, copper Cu and zinc Zn; preferably, said B is selected from one or two positive trivalent said fourth period transition metal elements, or said B is selected from one positive divalent and one positive tetravalent said fourth period transition metal element.
In a specific embodiment, the electrolyte layer CD 1-x M x O 3-δ C in the type material is selected from one or two of barium Ba, strontium Sr and calcium Ca; d is selected from any one or two of Ti, zr and Ce; m is selected from any one or two of Sc scandium, yttrium Y, chromium Cr, iron Fe, cobalt Co, lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb and lutetium Lu.
In a preferred embodiment, an anode transition layer is further included between the anode layer and the electrolyte layer; and/or a cathode transition layer is further included between the cathode layer and the electrolyte layer.
In a specific embodiment, the anode transition layer is comprised of an anode material and an electrolyte material, and the cathode transition layer is comprised of a cathode material and an electrolyte material.
In another aspect of the present invention, a method for preparing a proton conducting electrolyte-based solid oxide fuel cell, as described above, comprises the steps of:
1) Preparing a target material: respectively preparing an anode target, an electrolyte target and a cathode target;
2) Sputtering and depositing an anode layer, an electrolyte layer and a cathode layer on a substrate material sequentially through a magnetron sputtering process to obtain the solid oxide fuel cell device precursor; preferably, sequentially sputtering and depositing an anode layer, an anode transition layer, an electrolyte layer, a cathode transition layer and a cathode layer to obtain the solid oxide fuel cell device precursor;
3) And carrying out high-temperature sintering on the solid oxide fuel cell device precursor and reducing the device anode to obtain the solid oxide fuel cell.
In a specific embodiment, the targets are an anode target and a cathode target containing a pore-forming agent and an electrolyte target without a pore-forming agent, wherein the pore-forming agent is selected from carbon powder or starch, and the pore-forming agent accounts for 1-3%, preferably 2%, of the mass of the target; the anode target, the cathode target and the electrolyte target are respectively formed by uniformly mixing pore-forming agent and anode powder, pore-forming agent and cathode powder, and electrolyte material powder, carrying out isostatic compaction, and carrying out machining forming to obtain corresponding targets; more preferably, the isostatic pressing is two steps of cold isostatic pressing and hot isostatic pressing, wherein the cold isostatic pressing pressure is 100-200MPa, the time is 3-5 hours, and the temperature is room temperature to 200 ℃; the hot isostatic pressing pressure is 80-150MPa, the time is 2-4 hours, and the temperature is 600-1000 ℃.
In a specific embodiment, the anode transition layer is made by sputtering the anode target and electrolyte target simultaneously; the cathode transition layer is prepared by sputtering the cathode target material and the electrolyte target material at the same time.
In a specific embodiment, the anode layer prepared by magnetron sputtering has a thickness of 1-15 μm, the anode transition layer has a thickness of 1-15 μm, the electrolyte layer has a thickness of 1-15 μm, the cathode transition layer has a thickness of 1-15 μm, and the cathode layer has a thickness of 1-15 μm.
In a specific embodiment, the substrate material is a metal foam or a metal mesh; the temperature of the substrate deposited by magnetron sputtering is 100-500 ℃, the magnetron sputtering power is 100-200W, the sputtering time is 200-800 minutes, and the argon gas pressure is 0.3-3Pa.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention replaces the oxygen ion conduction type electrolyte material in the traditional SOFC with the proton conduction type electrolyte material, and the volume of protons is far smaller than that of oxygen ions, so that the ion conductivity of the same order of magnitude is realized, the temperature required by a proton conductor is 200-300 ℃ lower than that of the oxygen ion conductor, thereby being beneficial to realizing the low temperature of SOFC operation and expanding the application scene thereof.
2) The invention uses AA' B of double-layer perovskite structure for cathode materials (such as strontium doped lanthanum manganate LSM and strontium doped lanthanum iron cobaltate LSCF) in the traditional SOFC 2 O 6-δ The model crystal is replaced to cooperate with the proton conduction electrolyte material to ensure that the whole device has better thermal expansion matching property and smaller interface impedance.
3) The main place where the electrochemical reaction of the whole device prepared by the present invention occurs changes from the anode portion of the conventional SOFC to the cathode portion of the present invention. Due to the change of materials, the cathode layer is further thinned and the consumption of cathode materials is reduced, so that the internal impedance of the single cell is further reduced, and the working temperature of the single cell is further reduced; and because hydrogen is used as fuel gas, the generation of carbon deposition in the traditional SOFC device is avoided, and the service life of the device is further prolonged.
4) According to the invention, the anode target material and the cathode target material containing the pore-forming agent are prepared, a magnetron sputtering mode is adopted to prepare the single cell device structure, the pore-forming agent is used as a part of the sputtering target material, in the sputtering film forming process, low-melting-point starch can be sublimated directly due to the instant high temperature of an electric arc, or carbon powder can be vaporized and changed into carbon dioxide to be discharged, holes are formed at one time, and then a reaction interface, namely a three-phase line, various organic auxiliary agents are not used in the whole preparation process, the environment is friendly, the process is simple, and the time consumption is greatly shortened.
5) The invention uses foam metal or metal net with excellent ductility and elasticity as a magnetron sputtering substrate material to replace the common cast nickel oxide ceramic substrate used in the conventional SOFC single cell preparation process, and the substrate material is used, so that on one hand, the performance of the device is considered, the device is compatible with the anode part of the device, and on the other hand, the phenomenon of film cracking possibly occurring when the magnetron sputtering is plated with a thick film of more than ten micrometers is overcome.
Drawings
FIG. 1 is a schematic diagram of the perovskite crystal (left cathode material, right electrolyte material) structure of the present invention.
Fig. 2 is a schematic diagram of a process flow for preparing a solid oxide fuel cell of the present invention.
Fig. 3 is a schematic diagram of a magnetron sputtering process of an SOFC single cell of the present invention.
Fig. 4 is a schematic view of a metal substrate material of the present invention.
Fig. 5 is a scanning electron micrograph of a cross-sectional sample of a SOFC device of example 1 of the present invention.
Fig. 6 is a scanning electron micrograph of a cross-sectional sample of a SOFC device of example 2 of the present invention.
Fig. 7 is a scanning electron micrograph of a cross-sectional sample of a SOFC device of example 3 of the present invention.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
As shown in FIG. 2, the preparation process flow of the solid oxide fuel cell of the invention is roughly divided into the steps of target material preparation, magnetron sputtering film formation, high-temperature sintering forming and reduction device anode, wherein the target material preparation comprises the steps of uniform powder mixing, isostatic compaction and machine tool processing forming.
Specifically, the process flow comprises the following steps:
1) Preparing a target material: respectively preparing an anode target, an electrolyte target and a cathode target;
2) Sputtering and depositing an anode layer, an electrolyte layer and a cathode layer on a substrate material sequentially through a magnetron sputtering process to obtain the solid oxide fuel cell device precursor; preferably, sequentially sputtering and depositing an anode layer, an anode transition layer, an electrolyte layer, a cathode transition layer and a cathode layer to obtain the solid oxide fuel cell device precursor;
3) And carrying out high-temperature sintering on the solid oxide fuel cell device precursor and reducing the device anode to obtain the solid oxide fuel cell.
In the step 1), the electrolyte target is prepared by preparing the targets, namely an anode target and a cathode target containing pore-forming agents, and the targets are prepared by adopting a two-step isostatic pressing method. In particular, a target material containing a pore-forming agent, wherein the pore-forming agent is selected from carbon powder or starch, and the pore-forming agent accounts for 1-3%, preferably 2%, of the mass of the target material; the anode target, the cathode target and the electrolyte target are respectively formed by uniformly mixing pore-forming agent and anode powder, pore-forming agent and cathode powder, and electrolyte material powder, carrying out isostatic compaction, and carrying out machining forming to obtain corresponding targets; more preferably, the isostatic pressing is two steps of cold isostatic pressing and hot isostatic pressing, wherein the cold isostatic pressing pressure is 100-200MPa, the time is 3-5 hours, and the temperature is room temperature to 200 ℃; the hot isostatic pressing pressure is 80-150MPa, the time is 2-4 hours, and the temperature is 600-1000 ℃.
Wherein the anode target is prepared by uniformly mixing nickel oxide NiO and a pore-forming agent, and then processing and forming by a two-step isostatic pressing method. The cathode target material is AA' B with a double-layer perovskite structure 2 O 6-δ The crystal material powder (shown in figure 1) and the pore-forming agent are uniformly mixed, and then the mixture is processed and molded by a two-step isostatic pressing method. The electrolyte target material is CD 1-x M x O 3-δ The perovskite structure proton conduction type electrolyte material powder (shown in figure 1) is prepared by a two-step isostatic pressing method, and the electrolyte target material does not contain a pore-forming agent, so that a compact electrolyte layer is prepared, and the performance of the SOFC single cell is improved. Specifically, the pore-forming agent generally has a particle diameter of 0.5-2 μmThe method comprises the steps of carrying out a first treatment on the surface of the The specific surface area of the anode powder is 1-5m 2 Specific surface area of cathode powder is 10-15m 2 Specific surface area of electrolyte material is 10-15m 2 /g。
In step 2), corresponding material layers are deposited by adopting corresponding targets through magnetron sputtering, as shown in fig. 3, anode targets are adopted to sputter anode layers in sequence, anode targets and electrolyte targets are adopted to sputter anode transition layers, electrolyte targets are adopted to sputter electrolyte layers, cathode targets and electrolyte targets are adopted to sputter cathode transition layers, and cathode targets are adopted to sputter cathode layers.
Wherein, the thickness of the anode layer prepared by magnetron sputtering is 1-15 mu m, the thickness of the anode transition layer is 1-15 mu m, the thickness of the electrolyte layer is 1-15 mu m, the thickness of the cathode transition layer is 1-15 mu m, and the thickness of the cathode layer is 1-15 mu m. Correspondingly, the temperature of the substrate for magnetron sputtering deposition of each layer is 100-500 ℃, the magnetron sputtering power is 100-200W, the sputtering time is 200-800 minutes, and the argon gas pressure is 0.3-3Pa.
In addition, the magnetron sputtering substrate material is selected from foam metal or metal mesh, such as porous metal nickel mesh or foam metal nickel, as shown in fig. 4, but not limited thereto. The casting nickel oxide ceramic substrate is replaced by using foam metal or metal net with excellent ductility and elasticity as a magnetron sputtering substrate material to replace the common casting nickel oxide ceramic substrate used in the conventional SOFC single cell preparation process, and the substrate material is used for considering the performance of the device on one hand, and the anode part of the device is excellent in compatibility, and on the other hand, the phenomenon of film cracking possibly occurring when the magnetron sputtering plating is more than ten microns thick film is also overcome.
Meanwhile, in the conventional SOFC manufacturing process, a reaction interface, i.e., three-phase line (interface between anode material, electrolyte material, fuel gas or interface between cathode material, electrolyte material, oxygen) inside the single cell anode layer and the cathode layer is formed by a pore-forming agent, and a pore-forming agent such as carbon powder or starch is added into casting or screen printing slurry, and then burned cleanly to form holes in the sintering process. In the invention, a single cell structure is prepared by adopting a magnetron sputtering mode, a pore-forming agent is used as a part of a sputtering target material, and in the sputtering film forming process, low-melting-point starch can be directly sublimated due to the instantaneous high temperature of an electric arc, or carbon powder can be gasified into carbon dioxide to be discharged, holes are formed at one time, and a reaction interface, namely a three-phase line, is formed, various organic auxiliary agents are not used in the whole preparation process, the environment is friendly, the process is simple, and the time consumption is greatly shortened.
In the step 3), the device after sputtering is transferred into a high-temperature sintering furnace for high-temperature sintering molding, the sintering temperature is 1000-1400 ℃, the sintering time is 1-2 hours, the heating rate is 3-5 hours, the cooling rate is 3-5 hours, and the interface bonding force between the device layers is enhanced through high-temperature sintering. After cooling, transferring the device into an annealing furnace, introducing nitrogen-hydrogen mixed gas (hydrogen accounts for 5 percent) at 600-900 ℃, keeping the SOFC single cell sheet for 2-4 hours in the reducing atmosphere, and completely reducing the nickel oxide component into a metallic nickel catalyst to prepare the solid oxide fuel cell based on proton conduction electrolyte.
The scanning electron microscope photograph of the structural interface of the SOFC device is shown in fig. 7, and is divided into an anode layer (NiO), an electrolyte layer (SZTS) and a cathode layer (SBCN), wherein the joint of the anode layer and the electrolyte layer comprises both anode materials and electrolyte materials, namely an anode transition layer (SZTS+NiO) or a composite layer, and the joint of the cathode layer and the electrolyte layer comprises both cathode materials and electrolyte materials, namely a cathode transition layer (SBCN+SZTS) or a composite layer.
Based on the characteristics of the materials, the electrochemical reaction of the whole device mainly changes from the anode part of the traditional SOFC to the cathode part in the invention. In a conventional SOFC single cell, oxygen is converted into oxygen ions through the catalytic action of a cathode material, and the oxygen ions reach the anode to react with fuel gas at the three-phase line interface of the anode part through the conduction action of an oxygen ion conduction electrolyte material; in the invention, the electrolyte type is changed, so that the conduction direction of the current carrier is changed, hydrogen is changed into protons under the catalysis of the anode material, the protons reach the cathode through the conduction of the proton conductor to react with oxygen at the three-phase line of the cathode part to release chemical energy, and the chemical energy is further converted into electric energy, and the materials are changed, so that the cathode layer is further thinned and the consumption of the cathode material is reduced, the internal impedance of the single cell is further reduced, and the working temperature of the single cell is further reduced; and because hydrogen is used as fuel gas, the problem of carbon deposition in the traditional internal reforming SOFC single cell caused by using hydrocarbon fuels such as methane is avoided, and the service life of the device is further prolonged.
It is well known to those skilled in the art that once the carbon deposition phenomenon occurs, carbon monoxide and hydrogen can be formed by reacting with the carbon deposition through steam in the condition of not serious in the early stage to discharge the carbon deposition, but if the carbon deposition amount exceeds the steam reforming capability, the carbon deposition is deposited and proliferated in the holes of the anode to fill the holes, thereby causing the anode to crack, the device to fail and seriously affecting the service life of the device.
The preparation process of the present invention is further illustrated by the following more specific examples, without any limitation.
Raw materials used in the experiment: the anode, electrolyte and cathode oxide powders were purchased from kcearcell corporation in korea.
Magnetron sputtering apparatus used in the examples: shen Keyi JPG450.
The SOFC cell performance test adopts: cutting the formed square single cell into button single cell pieces with the diameter of 2 cm by using a laser cutting machine, placing the button single cell pieces into a ProboStat high-temperature sample clamp, placing the high-temperature sample clamp into a Tianjin middle-ring 1200-degree vertical tubular electric furnace, introducing a lead into an Ivium-n-stat electrochemical workstation, and testing a discharge curve.
Example 1
The specific surface area is 1-3m 2 And (3) uniformly mixing per gram of NiO powder and carbon powder with the particle size of 0.5-1 mu m accounting for 3% of the mass percentage in a dry mixer, and preparing the anode NiO sputtering target by using a two-step isostatic pressing method. The pressure was kept at 130MPa for 4 hours at 100℃during cold isostatic pressing, 80MPa for 3 hours at 800℃and argon as a shielding gas during hot isostatic pressing.
Specific surface area 10-12m 2 BaCe/g 0.6 Zr 0.3 Y 0.1 O 3-δ The powder was used to prepare an electrolyte BCZY sputter target using a two-step isostatic pressing process. The pressure was kept at 180MPa for 5 hours at 150℃during cold isostatic pressing, at 100MPa for 2.5 hours at 1000℃under argon as a shielding gas.
The specific surface area is 10-15m 2 Per gram PrBaCo 2 O 6-δ The powder and the carbon powder with the particle size of 0.5-1 mu m accounting for 3 percent of the mass percentage are uniformly mixed in a dry mixer, and then the cathode PBC sputtering target is manufactured by a two-step isostatic pressing method. The pressure was kept at 150MPa for 4 hours at 120℃during cold isostatic pressing, at 100MPa for 3 hours at 900℃and argon as a shielding gas during hot isostatic pressing.
And placing a porous metal nickel screen on a magnetron sputtering sample table, and sequentially placing an anode NiO target, an electrolyte BCZY target and a cathode PBC target on the target. Firstly, preparing an anode layer, wherein in the sputtering process, the substrate temperature is kept at 150 ℃, the magnetron sputtering power is 100W, the argon pressure is kept at 0.5Pa, and the sputtering time is 400 minutes. Then, an electrolyte layer was prepared, during the sputtering, the deposition temperature was maintained at 200℃and the sputtering power was maintained at 150W, and the argon pressure was maintained at 0.5Pa for 200 minutes. Finally preparing a cathode layer, wherein in the sputtering process, the bottom temperature is kept at 150 ℃, the magnetron sputtering power is 120W, the argon pressure is kept at 0.5Pa, and the sputtering time is 400 minutes.
Transferring the sputtered target material into a high-temperature sintering furnace to sinter for 1 hour at the high temperature of 1400 ℃, heating for 5 hours, cooling for 5 hours, and strengthening the interface bonding force between the device layers. After the temperature reduction is completed, the device is transferred into an annealing furnace, nitrogen-hydrogen mixed gas (hydrogen accounts for 5 percent) is introduced at 700 ℃, the SOFC single cell is kept for 3 hours in the reducing atmosphere, and all nickel oxide components in the SOFC single cell are reduced into a metallic nickel catalyst. The SOFC single cell scanning electron microscopy test prepared is shown in fig. 5 (anode layer and cathode layer boundaries are not fully shown), with an anode layer thickness of about 10 μm, an electrolyte layer thickness of about 3 μm, and a cathode layer thickness of about 10 μm.The SOFC single cell has an open circuit voltage of 1.01V and a power of 0.43W/cm at 500 DEG C 2 。
Example 2
Specific surface area of 3-5m 2 And (3) uniformly mixing per gram of NiO powder and carbon powder with the particle size of 0.5-1.5 mu m accounting for 1% of the mass percentage in a dry mixer, and preparing the anode NiO sputtering target by using a two-step isostatic pressing method. The pressure was kept at 180MPa for 3 hours at 150℃during cold isostatic pressing, at 130MPa for 3.5 hours at 700℃and argon as a shielding gas during hot isostatic pressing.
The specific surface area is 12-15m 2 BaCe/g 0.5 Zr 0.4 Nd 0.1 O 3-δ The powder was used to prepare an electrolyte BCZN sputter target using a two-step isostatic press process. The pressure was kept at 200MPa for 4 hours at 160℃during cold isostatic pressing, at 140MPa for 3 hours at 800℃and argon as a shielding gas during hot isostatic pressing.
Specific surface area of 10-13m 2 GdBaCuFeO/g 6-δ The powder and the carbon powder with the particle size of 0.5-1.5 mu m accounting for 1 percent of the mass percentage are uniformly mixed in a dry mixer, and then the cathode GBCF sputtering target material is manufactured by a two-step isostatic pressing method. The pressure was maintained at 170MPa at 150℃for 3 hours, the pressure was maintained at 90MPa for 3.5 hours, and the temperature was maintained at 800℃with argon as a shielding gas during hot isostatic pressing.
And placing a porous metal nickel screen on a magnetron sputtering sample table, and sequentially placing an anode NiO target, an electrolyte BCZN target and a cathode GBCF target on the target. Firstly, preparing an anode layer, wherein in the sputtering process, the substrate temperature is kept at 250 ℃, the magnetron sputtering power is 130W, the argon pressure is kept at 1.5Pa, and the sputtering time is 500 minutes. Then preparing an anode transition layer, wherein in the sputtering process, the bottom temperature is kept at 280 ℃, the magnetron sputtering power of the electrolyte and the anode targets is respectively 180W and 130W, the argon gas pressure is kept at 1.5Pa, and the sputtering time is 200 minutes. Then, an electrolyte layer was prepared, during the sputtering, the deposition temperature was maintained at 300℃and the sputtering power was 180W, and the argon pressure was maintained at 1.5Pa for 200 minutes. Finally preparing a cathode layer, wherein in the sputtering process, the bottom temperature is kept at 250 ℃, the magnetron sputtering power is 150W, the argon pressure is kept at 1.5Pa, and the sputtering time is 500 minutes.
Transferring the sputtered target material into a high-temperature sintering furnace to sinter at 1200 ℃ for 1.5 hours, heating for 4 hours, cooling for 5 hours, and strengthening the interface bonding force between the device layers. After cooling, the device was transferred to an annealing furnace, and at 600 ℃, a nitrogen-hydrogen mixture (5% hydrogen) was introduced, and the SOFC cell was kept in the reducing atmosphere for 3 hours, and all the nickel oxide components therein were reduced to a metallic nickel catalyst. The SOFC single cell scanning electron microscopy test prepared is shown in fig. 6 (anode layer and cathode layer boundaries are not fully shown), with an anode layer of about 12 μm, an anode transition layer of about 2 μm, an electrolyte layer of about 2 μm, and a cathode layer of about 12 μm. The SOFC single cell has an open circuit voltage of 1.04V and a power of 0.48W/cm at 550 DEG C 2 。
Example 3
The specific surface area is 1-5m 2 And (3) uniformly mixing 1-2 mu m-particle-size carbon powder accounting for 2% of the mass percentage of the per gram NiO powder in a dry mixer, and preparing the anode NiO sputtering target by using a two-step isostatic pressing method. The pressure was kept at 160MPa for 3 hours at 160℃during cold isostatic pressing, at 110MPa for 4 hours at 900℃and argon as a shielding gas during hot isostatic pressing.
Specific surface area of 10-13m 2 SrZr/g 0.6 Ti 0.3 Sc 0.1 O 3-δ The powder was used to prepare an electrolyte SZHS sputter target using a two-step isostatic pressing process. The pressure was maintained at 170MPa at 180℃for 3 hours during cold isostatic pressing, at 120MPa for 3.5 hours during hot isostatic pressing, at 900℃with argon as the shielding gas.
The specific surface area is 12-15m 2 SmBaCoNiO/g 6-δ Uniformly mixing the powder and carbon powder with the particle size of 1-2 mu m accounting for 2% of the mass percentage in a dry mixer, and preparing the cathode SBC by using a two-step isostatic pressing methodAnd N sputtering target materials. The pressure was kept at 120MPa for 3 hours at 140℃during cold isostatic pressing, at 130MPa for 2.5 hours at 700℃and argon as shielding gas during hot isostatic pressing.
And placing a porous metal nickel screen on a magnetron sputtering sample table, and sequentially placing an anode NiO target, an electrolyte SZTS target and a cathode SBCN target on the target position. Firstly, preparing an anode layer, wherein in the sputtering process, the substrate temperature is kept at 350 ℃, the magnetron sputtering power is 170W, the argon pressure is kept at 2Pa, and the sputtering time is 700 minutes. Then preparing an anode transition layer, wherein in the sputtering process, the bottom temperature is kept at 280 ℃, the magnetron sputtering power of the electrolyte and the anode targets is 120W and 140W respectively, the argon gas pressure is kept at 2Pa, and the sputtering time is 600 minutes. Then, an electrolyte layer was prepared, during the sputtering, the deposition temperature was maintained at 200℃and the sputtering power was 140W, and the argon pressure was maintained at 1.5Pa for 200 minutes. Then preparing a cathode transition layer, wherein in the sputtering process, the bottom temperature is kept at 200 ℃, the magnetron sputtering power of the electrolyte and the cathode is 140W and 170W, the argon pressure is kept at 1.5Pa, and the sputtering time is 300 minutes. Finally preparing a cathode layer, wherein in the sputtering process, the bottom temperature is kept at 350 ℃, the magnetron sputtering power is 180W, the argon pressure is kept at 2Pa, and the sputtering time is 700 minutes.
Transferring the sputtered target material into a high-temperature sintering furnace to sinter at 1300 ℃ for 1.5 hours, heating for 3 hours, cooling for 5 hours, and strengthening the interface bonding force between the device layers. After cooling, the device was transferred to an annealing furnace, and at 800 ℃, a nitrogen-hydrogen mixture (5% hydrogen) was introduced, and the SOFC single cell was kept in the reducing atmosphere for 4 hours, and all the nickel oxide components therein were reduced to a metallic nickel catalyst. The SOFC single cell scanning electron microscopy test prepared is shown in fig. 7 (anode and cathode layer boundaries are not fully shown), with an anode layer of about 10 μm, an anode transition layer of about 10 μm, an electrolyte layer of about 3 μm, a cathode transition layer of 3 μm, and a cathode layer of about 10 μm. The SOFC single cell has an open circuit voltage of 0.99V and a power of 0.55W/cm at 500 DEG C 2 。
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (12)
1. A method for preparing a proton conducting electrolyte-based solid oxide fuel cell, comprising the steps of:
1) Preparing a target material: respectively preparing an anode target, an electrolyte target and a cathode target; the targets are anode targets and cathode targets containing pore-forming agents and electrolyte targets without pore-forming agents;
2) Sputtering and depositing an anode layer, an electrolyte layer and a cathode layer on a substrate material sequentially through a magnetron sputtering process to obtain the solid oxide fuel cell device precursor; the substrate material is foam metal or metal net;
3) Sintering the solid oxide fuel cell device precursor at a high temperature, and reducing the device anode to obtain the solid oxide fuel cell based on proton conduction type electrolyte;
wherein the proton conduction type electrolyte-based solid oxide fuel cell comprises a nickel oxide NiO porous anode layer, a dense electrolyte layer and a porous cathode layer, wherein the cathode layer adopts AA' B with a double-layer perovskite structure 2 O 6-δ A type crystal material, wherein A is any one or two of La series rare earth metal elements, A' is barium Ba, B is any one or two of fourth period transition metal elements, and delta represents the number of oxygen defects in a single unit cell;
the electrolyte layer adopts a structure of CD 1-x M x O 3-δ Proton conductive electrolyte material of perovskite structure, wherein C is any one or two of divalent alkaline earth metal elements, D is any one or two of tetravalent transition metal or rare earth metal elements, M is any one of trivalent transition metal elements or rare earth metal elementsOr two, wherein x represents the number of doping atoms M occupying the D-bit in a single unit cell, and is between 0 and 1; delta represents the number of oxygen defects in a single unit cell.
2. The method for producing a proton conducting electrolyte based solid oxide fuel cell as claimed in claim 1, wherein the cathode layer AA' B 2 O 6-δ The A in the crystal material is selected from one or two of La, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu; b is selected from scandium Sc, titanium Ti, chromium Cr, manganese Mn, iron Fe, cobalt Co, nickel Ni, copper Cu and zinc Zn.
3. The method for producing a proton conductive electrolyte-based solid oxide fuel cell as claimed in claim 1, wherein the electrolyte layer CD 1-x M x O 3-δ C in the type material is selected from one or two of barium Ba, strontium Sr and calcium Ca; d is selected from any one or two of Ti, zr and Ce; m is selected from any one or two of Sc scandium, yttrium Y, chromium Cr, iron Fe, cobalt Co, lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb and lutetium Lu.
4. The method for producing a proton conducting electrolyte based solid oxide fuel cell as claimed in claim 1, wherein an anode transition layer is further included between the anode layer and the electrolyte layer; and/or a cathode transition layer is further included between the cathode layer and the electrolyte layer.
5. The method for producing a proton conducting electrolyte based solid oxide fuel cell as claimed in claim 4, wherein the anode transition layer is composed of an anode material and an electrolyte material, and the cathode transition layer is composed of a cathode material and an electrolyte material.
6. The method for producing a proton conducting electrolyte based solid oxide fuel cell as claimed in claim 4, wherein the anode layer, the anode transition layer, the electrolyte layer, the cathode transition layer, and the cathode layer are sequentially sputter deposited to obtain a solid oxide fuel cell device precursor including the anode transition layer and the cathode transition layer.
7. The method for preparing a proton conducting electrolyte-based solid oxide fuel cell according to claim 1, wherein the pore-forming agent is selected from carbon powder or starch, and the pore-forming agent accounts for 1-3% of the target material by mass; the anode target, the cathode target and the electrolyte target are respectively formed by uniformly mixing pore-forming agent and anode powder, uniformly mixing pore-forming agent and cathode powder, and uniformly compacting electrolyte material powder, and then obtaining the corresponding targets through machining and forming.
8. The method for producing a proton conducting electrolyte based solid oxide fuel cell as claimed in claim 7, wherein the pore-forming agent is 2% by mass of the target.
9. The method for producing a proton conducting electrolyte based solid oxide fuel cell according to claim 7, wherein the isostatic pressing is two steps of cold isostatic pressing and hot isostatic pressing, wherein the cold isostatic pressing pressure is 100-200MPa, the time is 3-5 hours, and the temperature is room temperature to 200 ℃; the hot isostatic pressing pressure is 80-150MPa, the time is 2-4 hours, and the temperature is 600-1000 ℃.
10. The method for producing a proton conducting electrolyte based solid oxide fuel cell as claimed in claim 6, wherein the anode transition layer is formed by sputtering the anode target and the electrolyte target simultaneously; the cathode transition layer is prepared by sputtering the cathode target material and the electrolyte target material at the same time.
11. The method for preparing a proton conducting electrolyte based solid oxide fuel cell according to claim 6, wherein the thickness of the anode layer prepared by magnetron sputtering is 1-15 μm, the thickness of the anode transition layer is 1-15 μm, the thickness of the electrolyte layer is 1-15 μm, the thickness of the cathode transition layer is 1-15 μm, and the thickness of the cathode layer is 1-15 μm.
12. The method for preparing a proton conductive electrolyte-based solid oxide fuel cell according to claim 1, wherein the substrate temperature of the magnetron sputtering deposition is 100-500 ℃, the magnetron sputtering power is 100-200W, the sputtering time is 200-800 minutes, and the argon gas pressure is 0.3-3Pa.
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| CN108630949A (en) * | 2018-03-22 | 2018-10-09 | 潮州三环（集团）股份有限公司 | A kind of solid oxide fuel cell and preparation method thereof |
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