CN112768704A - Solid oxide fuel cell based on proton conduction type electrolyte and preparation method - Google Patents
Solid oxide fuel cell based on proton conduction type electrolyte and preparation method Download PDFInfo
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Abstract
The invention discloses a solid oxide fuel cell based on proton conduction type electrolyte and a preparation method thereof, which uses CD as an electrolyte material in the traditional SOFC single cell1‑xMxO3‑δSubstitution of proton-conducting electrolyte material with perovskite structure, and AA' B used in combination2O6‑δThe anode layer and the cathode layer of the SOFC single cell are both prepared by adopting a metal oxide target material containing a pore-forming agent through magnetron sputtering, and the electrolyte layer is made of gold without the pore-forming agentThe oxide target material is prepared by magnetron sputtering. The method has the advantages of wide material selection, simple preparation process, no use of organic solvents, binders, plasticizers, activators, other organic auxiliaries and the like in the whole process, and belongs to environment-friendly processing and 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 proton conduction electrolyte-based solid oxide fuel cell 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 portion dominates the reaction of the entire cell, but the LSM (strontium-doped lanthanum manganate) and LSCF (strontium-doped lanthanum iron cobaltate) materials used in the conventional SOFC single cell have relatively low catalytic activity and ionic conductivity, thus greatly affecting the performance of the entire cell.
The traditional SOFC single cell based on the oxygen ion conduction type electrolyte has the defects of high working temperature (650-850 ℃), large internal impedance, easy carbon deposition generation 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. Researchers have subsequently developed a solid oxide fuel cell based on proton conducting electrolyte materials that are protons, i.e., hydrogen ions. In the working process of the fuel cell taking the proton conductor material as the electrolyte, fuel gas is dissociated into protons and electrons after being catalyzed by the anode, the protons and the electrons reach the cathode through the proton conduction type electrolyte and an external circuit respectively, and the protons react with oxygen ions on one side of the cathode to generate water, so that external power supply is realized. In the proton-conducting electrolyte material, the electrochemical reaction of the anode part dominates the electrochemical reaction of the whole battery, so that the problem of low catalytic activity of the cathode material on oxygen can be effectively solved, and the reaction temperature is reduced.
However, the conventional preparation process of the SOFC device based on any conductive electrolyte material is the traditional process based on 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 experimenters are seriously influenced.
Disclosure of Invention
The invention aims to overcome 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 also aims to provide the preparation method of the solid oxide fuel cell based on the proton conduction electrolyte, which adopts magnetron sputtering without introducing organic auxiliary agent in the whole preparation process to prepare single cell devices, and has short time consumption and easy operation in the whole process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a solid oxide fuel cell based on a proton conducting electrolyte comprising a nickel oxide NiO porous anode layer, a dense electrolyte layer and a porous cathode layer, characterized in that the cathode layer comprises AA' B having a double layer perovskite structure2O6-δA crystalline material of the form wherein a is one or two of lanthanum La-based rare earth metal elements, a' is barium Ba, and B is one or two of fourth period transition metal elements;
the electrolyte layer comprises a material having a structure of CD1-xMxO3-δThe proton conduction type electrolyte material with the perovskite structure is characterized in that C is one or two of divalent alkaline earth metal elements, D is one or two of tetravalent transition metal elements or rare earth metal elements, and M is one or two of trivalent transition metal elements or rare earth metal elements, wherein x represents the number of doping atoms M occupying D position in a single unit cell and is between 0 and 1; δ represents the number of oxygen defects in a single unit cell.
In a specific embodiment, the cathode layer AA' B2O6-δA 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 any one or two of 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 of said fourth transition metal elements being trivalent and positive, or said B is selected from said fourth transition metal elements being divalent and tetravalentA periodic transition metal element.
In a specific embodiment, the electrolyte layer CD1-xMxO3-δC in the material is selected from any 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 one or two selected from 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 also arranged between the cathode layer and the electrolyte layer.
In a specific embodiment, 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.
In another aspect of the present invention, the foregoing method for preparing a proton conducting electrolyte-based solid oxide fuel cell includes 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 by a magnetron sputtering process in sequence to obtain the precursor of the solid oxide fuel cell device; preferably, an anode layer, an anode transition layer, an electrolyte layer, a cathode transition layer and a cathode layer are sequentially sputtered and deposited to obtain the precursor of the solid oxide fuel cell device;
3) and sintering the device precursor of the solid oxide fuel cell at high temperature, and reducing the anode of the device to obtain the solid oxide fuel cell.
In a specific embodiment, the target material is an anode target material and a cathode target material containing a pore-forming agent and an electrolyte target material containing no pore-forming agent, the pore-forming agent is selected from carbon powder or starch, and the pore-forming agent accounts for 1-3%, preferably 2%, of the target material by mass percent; the anode target, the cathode target and the electrolyte target are respectively and uniformly mixed by a pore-forming agent and anode powder, the pore-forming agent and cathode powder and electrolyte material powder, are compacted by isostatic pressing, and are machined and molded 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 between room temperature and 200 ℃; the hot isostatic 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 simultaneous sputtering of the anode target and electrolyte target; the cathode transition layer is formed by sputtering the cathode target material and the electrolyte target material simultaneously.
In a specific embodiment, 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.
In a specific embodiment, the backing material is a metal foam or a metal mesh; 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 pressure is 0.3-3 Pa.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, the oxygen ion conduction type electrolyte material in the traditional SOFC is replaced by 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, the low temperature of the SOFC operation is favorably realized, and the application scene of the SOFC operation is favorably expanded.
2) The invention uses the AA' B of double-layer perovskite structure as cathode material (such as strontium-doped lanthanum manganate LSM and strontium-doped lanthanum ferrocobalate LSCF) in the traditional SOFC2O6-δThe crystal substitute is matched with the proton conduction type electrolyte material to work, so that the device has better thermal expansion matching performance and smaller interface impedance.
3) The main sites where the electrochemical reactions take place for the entire device produced by the present invention have changed from the anode portion of a conventional SOFC to the cathode portion of the present invention. Due to the change of materials, the cathode layer is further thinned, the using amount of cathode materials is reduced, the internal resistance of a 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 and the cathode target containing the pore-forming agent are prepared, the single cell device structure is prepared by adopting a magnetron sputtering mode, the pore-forming agent is used as a part of the sputtering target, low-melting-point starch can be directly sublimated due to the instantaneous high temperature of electric arc in the sputtering film-forming process, or carbon powder can be vaporized into carbon dioxide to be discharged, holes are formed at one time, and then 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.
5) According to the invention, foam metal or metal mesh with excellent ductility and elasticity is used as a magnetron sputtering substrate material to replace a cast nickel oxide ceramic substrate frequently used in a conventional SOFC single cell preparation process, and the use of the substrate material not only considers the performance of a device and is extremely compatible with the anode part of the device, but also overcomes the film cracking phenomenon possibly generated when a dozen microns thick film is plated by magnetron sputtering.
Drawings
FIG. 1 is a schematic structural view of a perovskite crystal of the present invention (cathode material on the left, electrolyte material on the right).
Fig. 2 is a schematic flow diagram of a solid oxide fuel cell manufacturing process of the present invention.
Fig. 3 is a schematic diagram of the SOFC single cell sheet magnetron sputtering process of the present invention.
Fig. 4 is a schematic view of the metal substrate material of the present invention.
Fig. 5 is a scanning electron micrograph of a cross-sectional sample of the SOFC device of example 1 of the present invention.
Fig. 6 is a scanning electron micrograph of a cross-sectional sample of the SOFC device of example 2 of the present invention.
Fig. 7 is a scanning electron micrograph of a cross-sectional sample of the SOFC device of example 3 of the present invention.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
As shown in fig. 2, the process flow of the solid oxide fuel cell of the present invention is roughly divided into several steps of target material preparation, magnetron sputtering film formation, high-temperature sintering molding, and device anode reduction, wherein the target material preparation further includes the steps of powder uniform mixing, isostatic compaction, and machine tool machining molding.
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 by a magnetron sputtering process in sequence to obtain the precursor of the solid oxide fuel cell device; preferably, an anode layer, an anode transition layer, an electrolyte layer, a cathode transition layer and a cathode layer are sequentially sputtered and deposited to obtain the precursor of the solid oxide fuel cell device;
3) and sintering the device precursor of the solid oxide fuel cell at high temperature, and reducing the anode of the device to obtain the solid oxide fuel cell.
In the step 1), preparing the target material, namely preparing an electrolyte target material, an anode target material and a cathode target material containing the pore-forming agent, wherein the target material is prepared by adopting a two-step isostatic pressing method. In particular, the target material comprises 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 target material by mass percent; the anode target, the cathode target and the electrolyte target are respectively and uniformly mixed by a pore-forming agent and anode powder, the pore-forming agent and cathode powder and electrolyte material powder, are compacted by isostatic pressing, and are machined and molded 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 between room temperature and 200 ℃; the hot isostatic pressure is 80-150MPa, the time is 2-4 hours, and the temperature is 600-1000 ℃.
The anode target material is prepared by uniformly mixing nickel oxide NiO and a pore-forming agent and then reprocessing and forming the mixture by a two-step isostatic pressing method. The cathode target material is AA' B with a double-layer perovskite structure2O6-δThe crystal form material powder (shown in figure 1) and the pore-forming agent are uniformly mixed and then are processed and formed by a two-step isostatic pressing method to obtain the crystal form material. The electrolyte target is CD1-xMxO3-δThe proton conduction type electrolyte material powder with the perovskite structure (as 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 can be prepared, and the performance of an SOFC single cell can be improved. Specifically, the particle size of the pore-forming agent is generally 0.5 to 2 μm; the specific surface area of the anode powder is 1-5m2The specific surface area of the cathode powder is 10-15m2A specific surface area of the electrolyte material is 10-15m2/g。
In step 2), the corresponding material layer is deposited by magnetron sputtering using the corresponding target, as shown in fig. 3, the anode layer is sputtered using the anode target, the anode transition layer is sputtered using the anode target and the electrolyte target, the electrolyte layer is sputtered using the electrolyte target, the cathode transition layer is sputtered using the cathode target and the electrolyte target, and the cathode layer is sputtered using the cathode target.
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. Correspondingly, the substrate temperature of each layer of magnetron sputtering deposition is 100-500 ℃, the magnetron sputtering power is 100-200W, the sputtering time is 200-800 minutes, and the argon pressure is 0.3-3 Pa.
In addition, the substrate material for magnetron sputtering is selected from a metal foam or a metal mesh, such as a porous metal nickel mesh or a metal nickel foam, as shown in fig. 4, but not limited thereto. The use of the substrate material gives consideration to the performance of the device on one hand and has excellent compatibility with the anode part of the device on the other hand, and overcomes the film cracking phenomenon which can occur when the thick film of more than ten microns is plated by magnetron sputtering on the other hand.
Meanwhile, in the conventional SOFC preparation process, a reaction interface, i.e., a three-phase line (an interface between an anode material, an electrolyte material and fuel gas or an interface between a cathode material, an electrolyte material and oxygen gas) inside a single cell anode layer and a single cell cathode layer is formed by a pore-forming agent, and the pore-forming agent, such as carbon powder or starch, is added into casting or screen printing slurry and then is burnt cleanly to form pores in a sintering process. In the invention, a magnetron sputtering mode is adopted to prepare a single cell structure, the 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 electric arc, or carbon powder can be vaporized into carbon dioxide to be discharged, so that holes are formed at one time, and a reaction interface, namely a three-phase line, is further formed.
In the step 3), the device after sputtering is transferred into a high-temperature sintering furnace for high-temperature sintering molding, wherein the sintering temperature is usually 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 strengthened through high-temperature sintering. And after the temperature reduction is finished, transferring the device into an annealing furnace, introducing nitrogen-hydrogen mixed gas (hydrogen accounts for 5%) at the temperature of 600-900 ℃, keeping the SOFC single cell in the reducing atmosphere for 2-4 hours, and reducing all nickel oxide components in the SOFC single cell into a metallic nickel catalyst to obtain the solid oxide fuel cell based on the proton-conducting 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 includes both the anode material and the electrolyte material, and is called an anode transition layer (SZTS + NiO) or a composite layer, and the joint of the cathode layer and the electrolyte layer includes both the cathode material and the electrolyte material, and is called a cathode transition layer (SBCN + SZTS) or a composite layer.
Based on the characteristics of the above materials, the electrochemical reaction mainly occurs in the whole device from the anode portion of the conventional SOFC to the cathode portion of the present invention. In a conventional SOFC single cell, oxygen is converted into oxygen ions by the catalytic action of a cathode material, and the oxygen ions reach an anode by the conduction action of an oxygen ion conduction type electrolyte material to react with fuel gas at a three-phase line interface of an anode portion; in the invention, the electrolyte type is changed, so that the conduction direction of a current carrier is changed, hydrogen is changed into protons under the catalytic action of an anode material, the hydrogen reaches a cathode through the conduction action of a proton conductor and reacts with oxygen on a three-phase line of the cathode part to release chemical energy, and then the hydrogen is converted into electric energy; and because hydrogen is used as fuel gas, the problem of carbon deposition formed inside the conventional internal reforming SOFC single cell when 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 occurs, it may be discharged without serious problems by introducing steam to react with the carbon deposition to form carbon monoxide and hydrogen, but if the amount of carbon deposition exceeds the steam reforming capability, the carbon deposition will grow in the pores of the anode to fill the pores, thereby causing the anode to crack, and the device to fail, which seriously affects the lifetime of the device.
The preparation process according to the invention is further illustrated, without any limitation, by the following more specific examples.
Raw materials used in the experiment: anode, electrolyte and cathode oxide powders were purchased from Kceracell, korea.
Magnetron sputtering apparatus used in the examples: sinker JPG 450.
SOFC battery performance test adopts: cutting the formed square single cell into button-type single cell pieces with the diameter of 2 cm by using a laser cutting machine, putting the button-type single cell pieces into a Probost high-temperature sample clamp, putting the high-temperature sample clamp into a 1200-degree vertical tubular electric furnace in Tianjin, introducing a lead into an Ivium-n-stat electrochemical workstation, and testing a discharge curve.
Example 1
The specific surface area is 1 to 3m2And uniformly mixing NiO powder per gram and carbon powder with the grain diameter of 0.5-1 mu m accounting for 3 percent of the mass percent in a dry mixer, and preparing the anode NiO sputtering target material by using a two-step isostatic pressing method. The pressure is maintained at 130MPa at 100 deg.C for 4 hr in cold isostatic pressing, the pressure is maintained at 80MPa for 3 hr in hot isostatic pressing, and the temperature is maintained at 800 deg.C with argon as the protective gas.
The specific surface area is 10-12m2BaCe of/g0.6Zr0.3Y0.1O3-δThe powder was made into an electrolyte BCZY sputter target using a two-step isostatic pressing process. The pressure is kept at 180MPa and the temperature is 150 ℃ for 5 hours in cold isostatic pressing, the pressure is kept at 100MPa and the time is 2.5 hours in hot isostatic pressing, the temperature is kept at 1000 ℃, and argon is used as protective gas.
The specific surface area is 10-15m2PrBaCo of/g2O6-δAfter the powder and carbon powder with the grain diameter of 0.5-1 mu m accounting for 3 percent of the mass percentage are evenly mixed in a dry mixer, the cathode PBC sputtering target material is prepared by a two-step isostatic pressing method. The pressure is kept at 150MPa at 120 ℃ for 4 hours during cold isostatic pressing, the pressure is kept at 100MPa for 3 hours at 900 ℃ during hot isostatic pressing, and argon is used as protective gas.
And placing the 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 position. 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. And then preparing an electrolyte layer, wherein in the sputtering process, the bottom deposition temperature is kept at 200 ℃, the sputtering power is 150W, the argon pressure is kept at 0.5Pa, and the sputtering time is 200 minutes. And finally, preparing a cathode layer, wherein in the sputtering process, the bottom deposition 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.
And transferring the target material after sputtering to a high-temperature sintering furnace, sintering for 1 hour at the high temperature of 1400 ℃, heating for 5 hours, and cooling for 5 hours to strengthen the interface bonding force between the device layers. After the temperature reduction is finished, the device is transferred into an annealing furnace, nitrogen-hydrogen mixed gas (hydrogen accounts for 5%) is introduced at 700 ℃, the SOFC single cell is kept for 3 hours in the reducing atmosphere, and the nickel oxide component in the SOFC single cell is completely reduced into the metallic nickel catalyst. The prepared SOFC single cell is tested by scanning electron microscopy as shown in fig. 5 (the boundaries of the anode layer and the cathode layer are not fully shown), the anode layer is about 10 μm thick, the electrolyte layer is about 3 μm thick, and the cathode layer is about 10 μm thick. The SOFC single cell is tested to have the open-circuit voltage of 1.01V and the power of 0.43W/cm at 500 DEG C2。
Example 2
The specific surface area is 3-5m2And uniformly mixing NiO powder per gram and carbon powder with the grain diameter of 0.5-1.5 mu m accounting for 1 percent of the mass percent in a dry mixer, and preparing the anode NiO sputtering target by using a two-step isostatic pressing method. The pressure is kept at 180MPa and the temperature is 150 ℃ during cold isostatic pressing, the time is 3 hours, the pressure is kept at 130MPa and the time is 3.5 hours during hot isostatic pressing, the temperature is kept at 700 ℃, and argon is used as protective gas.
The specific surface area is 12-15m2BaCe of/g0.5Zr0.4Nd0.1O3-δThe powder was made into an electrolyte BCZN sputtering target using a two-step isostatic pressing process. The pressure was maintained at 200MPa at 160 ℃ for 4 hours during cold isostatic pressing, at 140MPa for 3 hours at 800 ℃ for hot isostatic pressing, and argon was used as a shielding gas.
The specific surface area is 10-13m2GdBaCuFeO in g6-δDry mixing the powder and carbon powder with grain diameter of 0.5-1.5 μm accounting for 1% of the weight percentageAfter being mixed uniformly in the machine, the cathode GBCF sputtering target material is prepared by a two-step isostatic pressing method. The pressure is kept at 170MPa and the temperature is 150 ℃ for 3 hours in cold isostatic pressing, the pressure is kept at 90MPa and the time is 3.5 hours in hot isostatic pressing, the temperature is kept at 800 ℃, and argon is used as protective gas.
And placing the porous metal nickel net 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 position. 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. And then preparing an anode transition layer, wherein the bottom deposition temperature is kept at 280 ℃ in the sputtering process, the magnetron sputtering power of the electrolyte target and the magnetron sputtering power of the anode target are respectively 180W and 130W, the argon pressure is kept at 1.5Pa, and the sputtering time is 200 minutes. And then preparing an electrolyte layer, wherein in the sputtering process, the bottom deposition temperature is kept at 300 ℃, the sputtering power is 180W, the argon pressure is kept at 1.5Pa, and the sputtering time is 200 minutes. And finally, preparing a cathode layer, wherein the bottom deposition temperature is kept at 250 ℃ in the sputtering process, the magnetron sputtering power is 150W, the argon pressure is kept at 1.5Pa, and the sputtering time is 500 minutes.
And transferring the target material after sputtering to a high-temperature sintering furnace, sintering at the high temperature of 1200 ℃ for 1.5 hours, heating for 4 hours, and cooling for 5 hours to strengthen the interface bonding force between the device layers. After the temperature reduction is finished, the device is transferred into an annealing furnace, nitrogen-hydrogen mixed gas (hydrogen accounts for 5%) is introduced at the temperature of 600 ℃, the SOFC single cell is kept for 3 hours in the reducing atmosphere, and the nickel oxide component in the SOFC single cell is completely reduced into the metallic nickel catalyst. The prepared SOFC single cell is tested by scanning electron microscopy as shown in fig. 6 (the boundaries of the anode layer and the cathode layer are not fully shown), with about 12 μm for the anode layer, about 2 μm for the anode transition layer, about 2 μm for the electrolyte layer, and about 12 μm for the cathode layer. The SOFC single cell is tested to have the open-circuit voltage of 1.04V and the power of 0.48W/cm at 550 DEG C2。
Example 3
The specific surface area is 1-5m2NiO powder per gram and carbon powder with 1-2 μm particle diameter accounting for 2% of massAfter being mixed uniformly in a dry mixer, the anode NiO sputtering target material is prepared by using a two-step isostatic pressing method. The pressure is kept at 160MPa and the temperature is kept at 160 ℃ for 3 hours in cold isostatic pressing, the pressure is kept at 110MPa and the time is kept at 4 hours in hot isostatic pressing, and the temperature is kept at 900 ℃ and argon is used as protective gas.
The specific surface area is 10-13m2(iv) SrZr of0.6Ti0.3Sc0.1O3-δThe powder was made into electrolyte SZHS sputtering target using a two-step isostatic pressing process. The pressure is kept at 170MPa and 180 ℃ for 3 hours in cold isostatic pressing, the pressure is kept at 120MPa and 3.5 hours in hot isostatic pressing, and the temperature is kept at 900 ℃ and argon is used as protective gas.
The specific surface area is 12-15m2SmBaCoNiO/g6-δAnd uniformly mixing the powder and carbon powder with the grain diameter of 1-2 mu m accounting for 2 percent of the mass percentage in a dry mixer, and preparing the cathode SBCN sputtering target material by using a two-step isostatic pressing method. The pressure is maintained at 120MPa at 140 deg.C for 3 hr in cold isostatic pressing, the pressure is maintained at 130MPa for 2.5 hr in hot isostatic pressing, and the temperature is maintained at 700 deg.C with argon as shielding gas.
And placing the porous metal nickel net 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. And then preparing an anode transition layer, wherein the bottom deposition temperature is kept at 280 ℃ in the sputtering process, the magnetron sputtering power of the electrolyte target and the magnetron sputtering power of the anode target are respectively 120W and 140W, the argon pressure is kept at 2Pa, and the sputtering time is 600 minutes. And then preparing an electrolyte layer, wherein the bottom deposition temperature is kept at 200 ℃, the sputtering power is 140W, the argon pressure is kept at 1.5Pa, and the sputtering time is 200 minutes. And then preparing a cathode transition layer, wherein the bottom deposition temperature is kept at 200 ℃ in the sputtering process, 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. And finally, preparing a cathode layer, wherein in the sputtering process, the bottom deposition temperature is kept at 350 ℃, the magnetron sputtering power is 180W, the argon pressure is kept at 2.Pa, and the sputtering time is 700 minutes.
And transferring the target material after sputtering to a high-temperature sintering furnace, sintering at 1300 ℃ for 1.5 hours, heating for 3 hours, and cooling for 5 hours to strengthen the interface bonding force between the device layers. After the temperature reduction is finished, the device is transferred into an annealing furnace, nitrogen-hydrogen mixed gas (hydrogen accounts for 5%) is introduced at 800 ℃, the SOFC single cell is kept for 4 hours in the reducing atmosphere, and the nickel oxide component in the SOFC single cell is completely reduced into the metallic nickel catalyst. The prepared SOFC single cell is tested by scanning electron microscope as shown in fig. 7 (the boundaries of the anode layer and the cathode layer are not completely shown), the anode layer is about 10 μm, the anode transition layer is about 10 μm, the electrolyte layer is about 3 μm, the cathode transition layer is 3 μm, and the cathode layer is about 10 μm. The SOFC single cell is tested to have the open-circuit voltage of 0.99V and the power of 0.55W/cm at 500 DEG C2。
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A solid oxide fuel cell based on proton conduction electrolyte comprises a nickel oxide NiO porous anode layer, a compact electrolyte layer and a porous cathode layer, and is characterized in that the cathode layer adopts AA' B with a double-layer perovskite structure2O6-δA crystalline material of the form wherein a is either one or two of lanthanum La-based rare earth metal elements, a' is barium Ba, B is either one or two of fourth-period transition metal elements, δ represents the number of oxygen defects in a single unit cell;
the electrolyte layer adopts a structural formula of CD1-xMxO3-δThe proton conductive electrolyte material with perovskite structure comprises C as one or two of divalent alkaline earth metal elements, and D as tetravalent transition metal or rare earth metal elementAny one or two of elements, M is one or two of trivalent transition metal elements or rare earth metal elements, wherein x represents the number of doping atoms M occupying D position in a single unit cell and is between 0 and 1; δ represents the number of oxygen defects in a single unit cell.
2. The proton conducting electrolyte based solid oxide fuel cell according to claim 1, wherein the cathode layer AA' B2O6-δA 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 any one or two of scandium Sc, titanium Ti, chromium Cr, manganese Mn, iron Fe, cobalt Co, nickel Ni, copper Cu and zinc Zn.
3. The proton-conducting electrolyte-based solid oxide fuel cell according to claim 1, wherein the electrolyte layer CD1-xMxO3-δC in the material is selected from any 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 one or two selected from 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 proton conducting electrolyte based solid oxide fuel cell according to claim 1, further comprising an anode transition layer between the anode layer and the electrolyte layer; and/or a cathode transition layer is also arranged between the cathode layer and the electrolyte layer.
5. The proton conducting electrolyte based solid oxide fuel cell according to claim 4, wherein 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.
6. A method of manufacturing a proton conducting electrolyte based solid oxide fuel cell according to any of claims 1 to 5, comprising 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 by a magnetron sputtering process in sequence to obtain the precursor of the solid oxide fuel cell device; preferably, an anode layer, an anode transition layer, an electrolyte layer, a cathode transition layer and a cathode layer are sequentially sputtered and deposited to obtain the precursor of the solid oxide fuel cell device;
3) and sintering the device precursor of the solid oxide fuel cell at high temperature, and reducing the anode of the device to obtain the solid oxide fuel cell.
7. The method according to claim 6, wherein the target materials are an anode target material and a cathode target material containing a pore-forming agent and an electrolyte target material containing no pore-forming agent, the pore-forming agent is selected from carbon powder or starch, and the mass percentage of the pore-forming agent in the target material is 1-3%, preferably 2%; the anode target, the cathode target and the electrolyte target are respectively and uniformly mixed by a pore-forming agent and anode powder, the pore-forming agent and cathode powder and electrolyte material powder, are compacted by isostatic pressing, and are machined and molded 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 between room temperature and 200 ℃; the hot isostatic pressure is 80-150MPa, the time is 2-4 hours, and the temperature is 600-1000 ℃.
8. The method of claim 6, wherein the anode transition layer is formed by sputtering the anode target and the electrolyte target simultaneously; the cathode transition layer is formed by sputtering the cathode target material and the electrolyte target material simultaneously.
9. The method for manufacturing a proton-conducting electrolyte-based solid oxide fuel cell according to any one of claims 6 to 8, wherein the magnetron sputtering is used to manufacture an anode layer having a thickness of 1 to 15 μm, an anode transition layer having a thickness of 1 to 15 μm, an electrolyte layer having a thickness of 1 to 15 μm, a cathode transition layer having a thickness of 1 to 15 μm, and a cathode layer having a thickness of 1 to 15 μm.
10. The method of claim 9, wherein the substrate material is a metal foam or a metal mesh; 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 pressure is 0.3-3 Pa.
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| CN116864760A (en) * | 2023-09-04 | 2023-10-10 | 中石油深圳新能源研究院有限公司 | Battery preparation method and battery |
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