A proton ceramic fuel half-cell containing a transition layer, a battery and a preparation method thereof

Abstract

The present invention provides a proton ceramic fuel half-cell, a cell, and a preparation method containing a transition layer. This relates to the field of solid oxide fuel cell technology and comprises: an oxygen ion conductor support layer; a transition layer, composited onto the oxygen ion conductor support layer and made from cerium-based ceramic powder; an anode functional layer, composited onto the transition layer using a proton conductor material; and an electrolyte layer, composited onto the anode functional layer. By designing a NiO / cerium oxide-based transition layer between the fuel electrode support layer and the fuel electrode functional layer, the formation of a difficult-to-sinter phase between the support layer and the functional layer is prevented, effectively resolving the problem of the formation of a zirconium-rich oxide layer, which makes battery sintering difficult and reduces the catalytic activity of the functional layer.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid oxide fuel cells, and in particular relates to a proton ceramic fuel half-cell containing a transition layer, a battery and a preparation method thereof. Background Art

[0002] Solid oxide cell (SOC) is a clean energy conversion device that can convert chemical energy directly into electrical energy and electrical energy into chemical energy. It has the dual functions of solid oxide fuel cells and solid oxide electrolyzers. Depending on the different ions conducted by the electrolyte material, SOC can be divided into oxygen ion conductor type batteries and proton conductor type batteries. Traditional oxygen ion conductor type batteries have been developed for many years, with mature preparation technology, excellent performance at high temperatures, and have been commercially used. However, as the operating conditions of SOC develop towards medium and low temperatures, proton conductor type batteries have received widespread attention due to their advantages such as low proton conduction activation energy, low operating temperature, and more flexible fuel selection.

[0003] However, proton conductor batteries are still immature. Their nickel / proton conductor electrolyte material fuel electrode support type batteries face problems with poor mechanical strength and toughness, posing a major challenge to battery size expansion and battery stack packaging. The Ni / YSZ support material commonly used in oxygen ion conductor batteries has the advantages of good toughness and high strength. However, if directly applied to proton conductor batteries, the YSZ material will produce side reactions with the proton conductor electrolyte material in the functional layer, such as BCZY, during the high-temperature sintering process, forming a side reaction layer that is difficult to sinter, affecting battery shrinkage and making it difficult to sinter the electrolyte into a dense layer. At the same time, the side reaction will also reduce the catalytic activity of the functional layer, affecting the electrochemical performance of the battery. In the prior art, for example, the invention patent with publication number CN116632303A discloses a proton ceramic fuel cell and its preparation method. By adding a proton anode transition layer between the oxygen ion anode support layer and the active proton anode layer, the element loss of the active proton anode layer and the proton electrolyte layer can be avoided. The element retention rate of the active proton anode layer and the proton electrolyte layer is higher, thereby improving the overall mechanical strength of the battery while improving its electrochemical performance. However, this method pre-reacts the anode transition layer with the oxygen ion anode support layer, and itself uses the proton anode transition layer as a consumable layer to reduce the generation of undesirable by-products by the reaction between the active proton anode layer and the proton electrolyte layer. In order to prevent the by-products from affecting the bonding between the support layer and the transition layer during the sintering process, this invention arranges the support layer and the transition layer into a porous structure to avoid stress concentration, and strictly controls the sintering process parameters to avoid the reaction between the transition layer and the support layer during the preparation process to generate a difficult-to-sinter phase, thereby causing cracks at the interface between the transition layer and the substrate, thereby reducing the mechanical bonding strength between the two. Summary of the Invention

[0004] To address the shortcomings of the prior art, the present invention provides a proton ceramic fuel half-cell, cell, and preparation method containing a transition layer. By designing a NiO / cerium oxide-based transition layer between the fuel electrode support layer and the fuel electrode functional layer, the formation of a difficult-to-sinter phase between the support layer and the functional layer is prevented, effectively addressing the problem of the formation of a zirconium-rich oxide layer that hinders sintering and reduces the catalytic activity of the functional layer.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] On the one hand, the present invention provides a proton ceramic fuel half-cell containing a transition layer, comprising: an oxygen ion conductor support layer; a transition layer, wherein the transition layer is composited on the oxygen ion conductor support layer, and the transition layer is prepared by cerium-based ceramic powder; an anode functional layer, wherein the anode functional layer is made of a proton conductor material and composited on the transition layer; and an electrolyte layer, wherein the electrolyte layer is composited on the anode functional layer.

[0007] Furthermore, the oxygen ion conductor material support layer is formed by mixing and sintering NiO powder and zirconium yttrium oxide powder, wherein the mass ratio of the NiO powder to the zirconium yttrium oxide powder is 1:(1-1.5).

[0008] Furthermore, the transition layer is formed by mixing and sintering NiO powder and cerium-based ceramic powder, wherein the mass ratio of the NiO powder to the cerium-based ceramic powder is (2.5-3.5):1.

[0009] Furthermore, the anode functional layer is formed by mixing and sintering NiO powder and proton conductor material powder, wherein the mass ratio of the NiO powder to the proton conductor material powder is (1.3-1.7):1.

[0010] Furthermore, the thickness of the transition layer is 10-100 μm.

[0011] Furthermore, the proton conductor material is BaZr 1-x-y Ce y Y x O 3-δ 、BaZr 1-x-y-z Ce z Y y Yb x O 3-δ One of the following, where 0 <x<1,0<y<1,0<z<1,0<δ<1。

[0012] On the other hand, the present invention discloses a proton ceramic fuel cell containing a transition layer, comprising: the above-mentioned proton ceramic fuel half-cell; a cathode functional layer, wherein the cathode functional layer is composited on the electrolyte layer of the proton ceramic fuel half-cell.

[0013] On the other hand, the present invention discloses a method for preparing the above-mentioned proton ceramic fuel cell, comprising: preparing a proton ceramic fuel half-cell body; preparing a cathode functional layer membrane on one side of the electrolyte membrane of the proton ceramic fuel half-cell body to obtain a proton ceramic fuel cell body; sintering the proton ceramic fuel cell body at a temperature of 1200-1600°C for 10-20 hours and then cooling it to obtain the proton ceramic fuel cell body.

[0014] Furthermore, preparing a proton ceramic fuel half-cell body includes: weighing NiO powder and zirconium yttrium oxide powder, and pressing them into an oxygen ion conductor support layer membrane at a pressure of not less than 50 MPa; laying a transition layer material powder on the oxygen ion conductor support layer membrane, and pressing and molding it at a pressure of not less than 70 MPa to prepare a transition layer membrane; laying an anode functional layer material powder on the transition layer, and pressing and molding it at a pressure of not less than 70 MPa to prepare an anode functional layer membrane; laying an electrolyte material powder on the anode functional layer, and pressing and molding it at a pressure of not less than 200 MPa to prepare an electrolyte layer membrane.

[0015] Furthermore, the preparation of the proton ceramic fuel half-cell body includes: preparing an oxygen ion conductor support layer membrane, a transition layer membrane, an anode functional layer membrane and an electrolyte layer membrane by tape casting; and subjecting the above-mentioned membranes to a multi-step hot isostatic pressing treatment of "oxygen ion conductor support layer membrane | transition layer membrane | anode functional layer membrane | electrolyte layer membrane".

[0016] Compared with the prior art, the technical solution provided by the present invention brings the following beneficial effects: the support layer prepared from the oxygen ion conductor material has good mechanical and mechanical properties, such as NiO / YSZ, but YSZ easily reacts with the proton conductor material during the sintering process to form a zirconium-rich oxide layer. For example, BZCY with a high Zr content is difficult to shrink. The shrinkage rate of the zirconium-rich oxide layer after sintering is less than 9%, which is significantly different from the shrinkage rate between the oxygen ion conductor support layer and the anode functional layer. As a result, cracks appear at the interface between the anode functional layer, the oxygen ion conductor support layer, and the zirconium-rich oxide layer during the sintering process. The prepared proton ceramic fuel cell has poor mechanical properties, and the catalytic activity of the functional layer is reduced due to the generation of an intermediate phase. The present application sets a transition layer, and the transition layer and the support layer, that is, the Ce-modified zirconium-rich oxide layer generated by the reaction of CeO2 and YSZ, has a shrinkage rate increased to 13%, which is comparable to the shrinkage rate of the oxygen ion conductor support layer and the anode functional layer, and will not produce cracks, and the mechanical strength and catalytic activity of the functional layer are high; secondly, in the process of preparing a proton ceramic material half-cell or battery, the Ce-modified zirconium-rich oxide layer generated by high-temperature sintering is below 800°C, which is the temperature required for the proton ceramic fuel cell proposed in the present application during operation. The structure and phase of the Ce-modified zirconium-rich oxide layer are stable, and there will be no phase degradation or change, so that the prepared proton ceramic fuel half-cell or battery operates stably, and the output power attenuation rate and mechanical stability are comparable to those of oxygen ion conductor type batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0018] Figure 1 A schematic diagram of the proton ceramic fuel half-cell structure provided by an embodiment of the present invention;

[0019] Figure 2 This is a SEM image of the proton ceramic fuel cell provided in Example 1 of the present invention;

[0020] Figure 3 This is an SEM image of the proton ceramic fuel cell after the reaction of CeO2 and YSZ provided in Example 1 of the present invention;

[0021] Figure 4 This is a SEM image of a proton ceramic fuel cell provided in Comparative Example 1 of the present invention;

[0022] Figure 5 This is an SEM image of the proton ceramic fuel cell after the reaction of YSZ and BCZY provided in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0023] To make the objectives, technical solutions, and advantages of the present invention more apparent, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. The specific implementation methods of the present invention are not limited to the specific embodiments given herein, and those skilled in the art may make similar improvements without departing from the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used are only for describing specific embodiments and do not limit the present invention.

[0025] The present invention provides a proton ceramic fuel half cell containing a transition layer, such as Figure 1 , including: an oxygen ion conductor support layer; a transition layer, the transition layer is composited on the oxygen ion conductor support layer, and the transition layer is prepared by cerium-based ceramic powder; an anode functional layer, the anode functional layer is made of a proton conductor material and composited on the transition layer; and an electrolyte layer, the electrolyte layer is composited on the anode functional layer.

[0026] The support layer prepared with oxygen ion conductor materials has good mechanical and mechanical properties, such as NiO / YSZ. However, YSZ easily reacts with proton conductor materials during sintering to form a zirconium-rich oxide layer. For example, BZCY with a high Zr content is difficult to shrink. The shrinkage rate of the zirconium-rich oxide layer after sintering is less than 9%, which is quite different from the shrinkage rate between the oxygen ion conductor support layer and the anode functional layer. As a result, cracks appear at the interface between the anode functional layer, the oxygen ion conductor support layer and the zirconium-rich oxide layer during the sintering process. The prepared proton ceramic fuel cell has poor mechanical properties, and the catalytic activity of the functional layer is reduced due to the generation of an intermediate phase. The present application sets a transition layer, and the transition layer and the support layer, that is, the Ce-modified zirconium-rich oxide layer generated by the reaction of CeO2 and YSZ, has a shrinkage rate increased to 13%, which is comparable to the shrinkage rate of the oxygen ion conductor support layer and the anode functional layer, and will not produce cracks, and the mechanical strength and catalytic activity of the functional layer are high; secondly, in the process of preparing a proton ceramic material half-cell or battery, the Ce-modified zirconium-rich oxide layer generated by high-temperature sintering is below 800°C, that is, during the operation of the proton ceramic fuel half-cell proposed in the present application, the Ce-modified zirconium-rich oxide layer has a stable structure and phase, and no phase degradation or change occurs, so that the prepared proton ceramic fuel half-cell or battery operates stably, and the output power attenuation rate and mechanical stability are comparable to those of oxygen ion conductor type batteries.

[0027] The cerium-based ceramic powder in the embodiment of the present invention can be CeO2, Ce 1-x Y x O2, Ce 1-x Zrx One of O2, where 0 <x<0.2。

[0028] Specifically, the oxygen ion conductor material support layer is formed by mixing and sintering NiO powder and zirconium yttrium oxide powder, wherein the mass ratio of the NiO powder to the zirconium yttrium oxide powder is 1:(1-1.5). The zirconium yttrium oxide can be YSZ, such as 3YSZ or 8YSZ. NiO not only has a sintering aid effect, but also can generate Ni particles in a reducing atmosphere to increase the conductivity of electrons. Secondly, this ratio is conducive to reacting with the transition layer to form a dispersed Ce-modified zirconium-rich oxide layer, further reducing the local generation of a high-zirconium oxide layer, which leads to cracks between the substrate and the NiO powder. In the embodiment of the present invention, the average particle size of the NiO powder is 0.01-0.10μm, and the average particle size of the zirconium yttrium oxide powder is 2-3μm.

[0029] Specifically, the transition layer is formed by mixing and sintering NiO powder and cerium-based ceramic powder, wherein the mass ratio of the NiO powder to the cerium-based ceramic powder is (2.5-3.5):1. The average particle size of the NiO powder is 0.01-0.10 μm, and the average particle size of the cerium-based ceramic powder is 1.0-1.5 μm. The mass of NiO is higher than that of the cerium-based ceramic powder. This is mainly due to the consideration that the NiO powder of the transition layer and the NiO powder of the support layer are compatible during the sintering process, on the one hand, to disperse the generated Ce-modified zirconium-rich oxide layer, and on the other hand, to sinter and densify the two without generating cracks.

[0030] Specifically, the anode functional layer is formed by mixing and sintering NiO powder and proton conductor material powder, wherein the mass ratio of the NiO powder to the proton conductor material powder is (1.3-1.7): 1. The average particle size of the NiO powder is 0.01-0.10 μm, and the average particle size of the zirconium yttrium oxide powder is 2-3 μm. The anode functional layer needs to form a good connection with the transition layer. On the one hand, the material of the anode functional layer will not react with the transition layer and only undergoes metallurgical bonding. Secondly, the NiO powder needs to be compatible with the NiO powder of the transition layer to coordinate the deformation between the two during the sintering process, and the prepared proton ceramic fuel cell needs to have good interlayer bonding strength.

[0031] It should be noted that the anode functional layer may or may not be added with a pore-forming agent based on actual needs. If a pore-forming agent is added, a conventional commercial product may be used.

[0032] Specifically, the thickness of the transition layer is 10 - 100 μm. The transition layer should not be too thick or too thin. If it is too thick, it will affect the thickness and strength of the support layer. Since this application is designed without increasing the thickness of the existing proton ceramic fuel cell, and an increase in thickness will lead to an increase in the cost of the proton ceramic fuel cell. However, it should not be too thin. During the subsequent sintering process, the sintering temperature can reach 1200 - 1400 °C and is held for 10 - 20 h. At this temperature, on the one hand, it ensures good sintering between the layers of the prepared proton ceramic fuel cell, and on the other hand, it avoids the change of the Ce-modified zirconium-rich oxide layer due to element diffusion. For example, Zr in YSZ diffuses into the anode functional layer and reacts with the proton conductor material, generating an undesired phase and reducing the activity of the anode functional layer.

[0033] In the embodiment of the present invention, the thickness of the prepared proton ceramic fuel half-cell is 300 - 900 μm, wherein the thickness of the fuel electrode support layer is 200 - 850 μm, the thickness of the fuel electrode transition layer is 10 - 100 μm, the thickness of the fuel electrode functional layer is 10 - 100 μm, and the thickness of the electrolyte layer is 1 - 50 μm.

[0034] Specifically, the proton conductor material is BaZr 1-x-y Ce y Y x O 3-δ 、BaZr 1-x-y-z Ce z Y y Yb x O 3-δ One of them, where 0 < x < 1, 0 < y < 1, 0 < z < 1, 0 < δ < 1. For the purpose of illustration, in the embodiment of the present invention, BCZYYb uses BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3, and BCZY uses BaCe 0.5 Zr 0.3 Y 0.2 O3.

[0035] The embodiment of the present invention also provides a proton ceramic fuel cell containing a transition layer, including: the above half-cell; a cathode functional layer, and the cathode functional layer is compounded on the electrolyte layer of the half-cell.

[0036] For the purpose of illustration, BCFZY is used to illustrate the cathode functional layer in the present invention. It should be noted that the cathode functional layer can also be other commonly used materials.

[0037] The embodiment of the present invention also provides a preparation method of the above proton ceramic fuel cell, including:

[0038] S1. Prepare a half-cell body.

[0039] There are two technical solutions for preparing half-cell bodies:

[0040] (1) Weighing NiO powder and zirconium yttrium oxide powder, and pressing them under a pressure of not less than 50 MPa to form an oxygen ion conductor support layer membrane; laying transition layer material powder on the oxygen ion conductor support layer membrane, and pressing and molding them under a pressure of not less than 70 MPa to prepare a transition layer membrane; laying anode functional layer material powder on the transition layer, and pressing and molding them under a pressure of not less than 70 MPa to prepare an anode functional layer membrane; laying electrolyte material powder on the anode functional layer, and pressing and molding them under a pressure of not less than 200 MPa to prepare an electrolyte layer membrane.

[0041] (2) The oxygen ion conductor support layer membrane, transition layer membrane, anode functional layer membrane and electrolyte layer membrane are prepared by tape casting; the above membranes are subjected to multi-step hot isostatic pressing according to the "oxygen ion conductor support layer membrane | transition layer membrane | anode functional layer membrane | electrolyte layer membrane" process to obtain the membrane. The hot isostatic pressing process is: maintaining at 50-85°C and a pressure of 10-60MPa for at least 30 minutes. Multi-step hot isostatic pressing is to add different membranes layer by layer and perform hot isostatic pressing. For example, the fuel electrode membrane and the electrolyte membrane are first subjected to hot isostatic pressing. After the hot isostatic pressing is completed, the oxygen electrode membrane is stacked on the other side of the electrolyte membrane and subjected to hot isostatic pressing. After the hot isostatic pressing is completed, an integrated skeleton green body is obtained.

[0042] The slurry used in tape casting is prepared by adding a binder, a plasticizer and a dispersant to the corresponding powder material, wherein 5%-20% of the total powder mass of the dispersant, 1%-10% of the total powder mass of the plasticizer and 5%-20% of the total powder mass of the binder are added and mixed evenly.

[0043] The above methods are all commonly used methods for making blanks, and all can prepare proton ceramic fuel cell blanks with excellent performance. However, it should be noted that in this application, the blanks are prepared first and then sintered uniformly. The temperature during heating treatment before sintering should not exceed 900°C to prevent the transition layer from being burned through in a high-temperature and long-term environment.

[0044] S2. Prepare a cathode functional layer membrane on one side of the electrolyte membrane of the half-cell body to obtain a cell body.

[0045] For example, in order to characterize the prepared proton ceramic fuel cell, the present invention adopts BCFZY (BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1O3) cathode, specifically, after adding a binder, a plasticizer and a dispersant to the BCFZY powder, an oxygen electrode slurry is obtained and a fuel electrode membrane is made. The membrane is prepared by a casting method, and can also be prepared by other methods. Screen printing is used here for exemplary illustration. In an embodiment of the present invention, a dispersant of 5%-20% of the total powder mass, a plasticizer of 1%-10% of the total powder mass and a binder of 5%-20% of the total powder mass are added and mixed. The dispersant is one or more of triethanolamine, sodium polyacrylate and polyethylene oxide; the plasticizer and binder are one or more of dioctyl phthalate, polyethylene glycol, polyvinyl alcohol and polyvinyl acetate.

[0046] S3. Sintering the battery blank at a temperature of 1200-1600° C. for 10-20 hours and then cooling the blank to obtain the battery blank.

[0047] Specifically, if a binder, plasticizer, and dispersant are used in this application, a debinding process is required. After debinding, sintering at 1200-1600°C for 10-20 hours is sufficient. Because the transition layer in this application is compatible with the substrate, even the phase generated by the reaction is compatible with the substrate on both sides, so the sintering process is relatively simple.

[0048] If debinding is required, heat the sample to 300-600℃ at a rate of no more than 10℃ / min and keep it for at least 30 minutes. Heat the sample to 1200-1600℃ at a rate of no more than 20℃ / min and keep it for 10-20 hours. Cool the sample at a rate of no more than 10℃ / min.

[0049] If debinding is not required, heat the sample to 1200-1600°C at a rate not exceeding 20°C / min and maintain for 10-20 hours, then cool the sample at a rate not exceeding 10°C / min.

[0050] The prepared solid oxide cell was characterized by injecting H2 into the fuel electrode and pure O2 into the oxygen electrode at 550°C. The long-term stability of the prepared full cell was tested for 1000 hours and the power decay value was measured. The prepared solid oxide cell was characterized in electrolysis mode at 650°C with a constant current density of 1.00Acm -2 The fuel electrode is injected with H2, and the oxygen electrode is injected with O2 / H2O. The degradation rate is calculated by collecting voltage information within 1000 hours.

[0051] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0052] Example 1

[0053] This embodiment provides a method for preparing a proton ceramic fuel cell, and a fuel cell obtained by using the preparation method, comprising:

[0054] S1. Prepare a half-cell body.

[0055] (1) NiO powder and (Y2O3) 0.03 (ZrO2) 0.97 The (3YSZ) powders were uniformly mixed in a mass ratio of 1:1 to obtain an oxygen ion conductor support layer powder. A preset amount of the oxygen ion conductor support layer powder was weighed and pressed into a tablet using a tablet press at 50 MPa.

[0056] (2) NiO powder and CeO2 powder are uniformly mixed in a mass ratio of 3:1 to obtain transition layer powder, a preset amount of transition layer powder is weighed and evenly spread on the support layer to be pressed, and the powder is pressed into shape using a tablet press at 75 MPa using a tablet press.

[0057] (3) NiO powder and BZCY powder were uniformly mixed at a mass ratio of 1.5:1 to obtain anode functional layer powder, a preset amount of anode functional layer powder was weighed and evenly spread on the pressed transition layer, and the powder was pressed into shape using a tablet press at 75 MPa using a tablet press.

[0058] (4) Weigh a preset mass of BZCY electrolyte powder and evenly spread it on the pressed functional layer, and press it into shape using a tablet press at 250 MPa to obtain a half-cell body.

[0059] S2, prepare a cathode functional layer membrane on one side of the electrolyte membrane of the half-cell body to obtain a battery body. Prepare BCFZY powder slurry, and use screen printing to prepare a cathode functional layer on the prepared half-cell body to obtain a battery body. The prepared battery body is as follows Figure 1 shown.

[0060] S3. Raise the temperature to 300°C at a rate of 10°C / min and keep warm for 30 min, raise the temperature to 1600°C at a rate of 20°C / min and keep warm for 10 h, and cool down at a rate of 10°C / min. The thickness of the transition layer at at least 6 positions of the prepared proton ceramic fuel cell is measured and the average value is taken. The thickness of the transition layer is measured to be 12 μm.

[0061] like Figure 2 and 3 As shown, the intermediate phase generated by the oxygen ion conductor support layer and the transition layer of the prepared proton ceramic fuel cell has high density, no cracks, and good mechanical properties.

[0062] Measurements show that the prepared proton ceramic fuel cell exhibits excellent long-term stability after a 1000-hour discharge at 550°C with a power degradation rate of 0.9%. Furthermore, the prepared solid oxide cell exhibits a degradation rate of 0.019 V / kh when used for water electrolysis.

[0063] Example 2

[0064] This embodiment provides a method for preparing a proton ceramic fuel cell, and a fuel cell obtained by using the preparation method, comprising:

[0065] S1. Prepare a half-cell body.

[0066] NiO powder and (Y2O3) 0.03 (ZrO2) 0.97 The (3YSZ) powders were uniformly mixed in a mass ratio of 1:1 to obtain an oxygen ion conductor support layer powder. A preset amount of the oxygen ion conductor support layer powder was weighed and pressed into a tablet using a tablet press at 50 MPa.

[0067] (2) NiO powder and CeO2 powder were uniformly mixed at a mass ratio of 2.5:1 to obtain transition layer powder. A preset amount of transition layer powder was evenly spread on the support layer to be pressed and formed, and the powder was pressed into shape using a tablet press at 75 MPa using a tablet press.

[0068] (3) NiO powder and BZCY powder were uniformly mixed at a mass ratio of 1.3:1 to obtain anode functional layer powder, a preset amount of anode functional layer powder was weighed and evenly spread on the pressed transition layer, and the powder was pressed into shape using a tablet press at 75 MPa using a tablet press.

[0069] (4) Weigh a preset mass of BZCY electrolyte powder and evenly spread it on the pressed functional layer, and press it into shape using a tablet press at 250 MPa to obtain a half-cell body.

[0070] S2. Prepare a cathode functional layer membrane on one side of the electrolyte membrane of the half-cell body to obtain a battery body. Prepare a BCFZY powder slurry and screen print a cathode functional layer on the prepared half-cell body to obtain a battery body.

[0071] S3. Heat to 300°C at a rate of 10°C / min and keep warm for 30 min, heat to 1200°C at a rate of 20°C / min and keep warm for 10 h, cool at a rate of 10°C / min, and the thickness of the transition layer is measured to be 10 μm.

[0072] The interphase formed between the oxygen ion conductor support layer and the transition layer of the prepared proton ceramic fuel cell exhibits high density, no cracks, and excellent mechanical properties. Measurements show that the prepared proton ceramic fuel cell exhibits a power decay of 0.5% after 1000 hours of discharge at 550°C, demonstrating excellent long-term stability. The prepared solid oxide cell exhibited a degradation rate of 0.031 V / kh when subjected to water electrolysis.

[0073] Example 3

[0074] This embodiment provides a method for preparing a proton ceramic fuel cell, and a fuel cell obtained by using the preparation method, comprising:

[0075] S1. Prepare a half-cell body.

[0076] NiO powder and (Y2O3) 0.03 (ZrO2) 0.97 The (3YSZ) powders were uniformly mixed in a mass ratio of 1:1.3 to obtain an oxygen ion conductor support layer powder. A preset amount of the oxygen ion conductor support layer powder was weighed and pressed into a tablet press at 50 MPa using a tablet press mold.

[0077] (2) NiO powder and CeO2 powder are uniformly mixed in a mass ratio of 3:1 to obtain transition layer powder, a preset amount of transition layer powder is weighed and evenly spread on the support layer to be pressed, and the powder is pressed into shape using a tablet press at 75 MPa using a tablet press.

[0078] (3) NiO powder and BZCY powder were uniformly mixed at a mass ratio of 1.5:1 to obtain anode functional layer powder, a preset amount of anode functional layer powder was weighed and evenly spread on the pressed transition layer, and the powder was pressed into shape using a tablet press at 75 MPa using a tablet press.

[0079] (4) Weigh a preset mass of BZCY electrolyte powder and evenly spread it on the pressed functional layer, and press it into shape using a tablet press at 250 MPa to obtain a half-cell body.

[0080] S2. Prepare a cathode functional layer membrane on one side of the electrolyte membrane of the half-cell body to obtain a battery body. Prepare a BCFZY powder slurry and screen print a cathode functional layer on the prepared half-cell body to obtain a battery body.

[0081] S3. Heat to 500°C at a rate of 10°C / min and keep warm for 30 min, heat to 1400°C at a rate of 20°C / min and keep warm for 15 h, cool at a rate of 10°C / min, and the thickness of the transition layer is measured to be 50 μm.

[0082] The interphase formed between the oxygen ion conductor support layer and the transition layer of the prepared proton ceramic fuel cell exhibits high density, no cracks, and excellent mechanical properties. Measurements show that the prepared proton ceramic fuel cell exhibits a power decay of 0.8% after 1000 hours of discharge at 550°C, demonstrating excellent long-term stability. The prepared solid oxide cell exhibited a degradation rate of 0.027 V / kh when subjected to water electrolysis.

[0083] Example 4

[0084] This embodiment provides a method for preparing a proton ceramic fuel cell, and a fuel cell obtained by using the preparation method, comprising:

[0085] S1. Prepare a half-cell body.

[0086] NiO powder and (Y2O3) 0.03 (ZrO2) 0.97 The (3YSZ) powders were uniformly mixed at a mass ratio of 1:1.5 to obtain an oxygen ion conductor support layer powder. A preset amount of the oxygen ion conductor support layer powder was weighed and pressed into a tablet using a tablet press at 50 MPa.

[0087] (2) NiO powder and CeO2 powder were uniformly mixed at a mass ratio of 3.5:1 to obtain transition layer powder. A preset amount of transition layer powder was evenly spread on the support layer to be pressed and formed, and the powder was pressed into shape using a tablet press at 75 MPa using a tablet press.

[0088] (3) NiO powder and BZCY powder were uniformly mixed at a mass ratio of 1.7:1 to obtain anode functional layer powder, a preset amount of anode functional layer powder was weighed and evenly spread on the pressed transition layer, and the powder was pressed into shape using a tablet press at 75 MPa using a tablet press.

[0089] (4) Weigh a preset mass of BZCY electrolyte powder and evenly spread it on the pressed functional layer, and press it into shape using a tablet press at 250 MPa to obtain a half-cell body.

[0090] S2. Prepare a cathode functional layer membrane on one side of the electrolyte membrane of the half-cell body to obtain a battery body. Prepare a BCFZY powder slurry and screen print a cathode functional layer on the prepared half-cell body to obtain a battery body.

[0091] S3. Raise the temperature to 600°C at a rate of no more than 10°C / min and keep warm for 30 minutes. Raise the temperature to 1600°C at a rate of 20°C / min and keep warm for 20 hours. Cool down at a rate of 10°C / min. The thickness of the transition layer is measured to be 100 μm.

[0092] The intermediate phase generated between the oxygen ion conductor support layer and the transition layer of the prepared proton ceramic fuel cell has high density, no cracks and good mechanical properties.

[0093] Measurements show that the prepared proton ceramic fuel cell exhibits excellent long-term stability, with a power decay of 1.1% after 1000 hours of discharge at 550°C. The degradation rate of the prepared solid oxide cell in water electrolysis was 0.033V / kh.

[0094] Example 5

[0095] This embodiment provides a method for preparing a proton ceramic fuel cell, and a fuel cell obtained by using the preparation method, comprising:

[0096] S1. Prepare a half-cell body.

[0097] NiO powder and (Y2O3) 0.03 (ZrO2) 0.97 The (3YSZ) powders were uniformly mixed in a mass ratio of 1:1 to obtain an oxygen ion conductor support layer powder. A preset amount of the oxygen ion conductor support layer powder was weighed and pressed into a tablet using a tablet press at 50 MPa.

[0098] (2) NiO powder and CeO2 powder are uniformly mixed in a mass ratio of 3:1 to obtain transition layer powder, a preset amount of transition layer powder is weighed and evenly spread on the support layer to be pressed, and the powder is pressed into shape using a tablet press at 75 MPa using a tablet press.

[0099] (3) NiO powder and BZCYYb powder were uniformly mixed at a mass ratio of 1.5:1 to obtain anode functional layer powder, a preset amount of anode functional layer powder was weighed and evenly spread on the pressed transition layer, and the powder was pressed into shape using a tablet press at 75 MPa using a tablet press.

[0100] (4) Weigh a preset mass of BZCYYb electrolyte powder and evenly spread it on the pressed functional layer, and press it into shape using a tablet press at 250 MPa to obtain a half-cell body.

[0101] S2. Prepare a cathode functional layer membrane on one side of the electrolyte membrane of the half-cell body to obtain a battery body. Prepare a BCFZY powder slurry and screen print a cathode functional layer on the prepared half-cell body to obtain a battery body.

[0102] S3. Raise the temperature to 600°C at a rate of no more than 10°C / min and keep warm for 30 minutes. Raise the temperature to 1600°C at a rate of 20°C / min and keep warm for 20 hours. Cool down at a rate of 10°C / min. The thickness of the transition layer is measured to be 100 μm.

[0103] The intermediate phase generated between the oxygen ion conductor support layer and the transition layer of the prepared proton ceramic fuel cell has high density, no cracks and good mechanical properties.

[0104] Measurements show that the prepared proton ceramic fuel cell exhibits excellent long-term stability, with a power degradation rate of 1.2% after 1000 hours of discharge at 550°C. The prepared solid oxide cell also exhibits a degradation rate of 0.041 V / kh when used for water electrolysis.

[0105] Comparative Example 1

[0106] Compared with Example 1, the difference is that the thickness of the prepared transition layer is 1 μm.

[0107] like Figure 3 and 4 As shown, the intermediate phase generated between the oxygen ion conductor support layer and the transition layer of the prepared proton ceramic fuel cell has low density, cracks, and poor mechanical properties.

[0108] Measurements show that the prepared proton ceramic fuel cell's power decays by 5.0% after 1000 hours of discharge at 550°C. The degradation rate of the prepared solid oxide cell in water electrolysis is 0.25V / kh.

[0109] Comparative Example 2

[0110] Compared with Example 2, the difference is that in step S3, the temperature is raised to 300°C at a rate of 10°C / min and kept at that temperature for 30 minutes, and then the temperature is raised to 1100°C at a rate of 20°C / min and kept at that temperature for 10 hours.

[0111] The prepared proton ceramic fuel cell has low metallurgical bonding strength between layers and low overall mechanical strength.

[0112] Comparative Example 3

[0113] Compared with Example 2, the difference is that in step S3, the temperature is raised to 300°C at a rate of 10°C / min and kept at that temperature for 30 minutes, and then the temperature is raised to 1600°C at a rate of 20°C / min and kept at that temperature for 22 hours.

[0114] The prepared proton ceramic fuel cell oxygen ion conductor support layer and transition layer generate cracks and have poor mechanical properties.

[0115] Example 4

[0116] Compared with Example 1, the difference is that NiO powder and (Y2O3) 0.03 (ZrO2) 0.97 (3YSZ) powders were uniformly mixed at a mass ratio of 1:0.8 to obtain oxygen ion conductor support layer powders.

[0117] The intermediate phase generated between the oxygen ion conductor support layer and the transition layer of the prepared proton ceramic fuel cell has low density, but has a small amount of cracks and deviations in mechanical properties.

[0118] It can be seen that the proton ceramic fuel cells prepared in Examples 1-5 have excellent long-term stability in both power generation mode and electrolysis mode. As shown in Example 1 and Comparative Example 1, when the transition layer thickness is relatively thin, the Zr element crosses the barrier layer and reacts with the proton conductor material, forming a zirconium-rich oxide layer. During sintering, when the thermal stress exceeds the local maximum allowable stress, more cracks appear. This results in poor mechanical properties and stability. Comparing Example 2 with Comparative Examples 2 and 3 shows that the thickness of the transition layer is related to the sintering process of the proton ceramic fuel cell. The sintering process forms a Ce-modified zirconium-rich oxide layer between the transition layer and the support layer. Insufficient sintering fails to improve the overall mechanical properties of the proton ceramic fuel cell. Excessive sintering causes Zr to penetrate the transition layer, resulting in the formation of a zirconium-rich oxide layer, which weakens the overall mechanical strength and performance. Comparing Example 1 and Comparative Example 4 shows that the NiO in each layer coordinates the deformation between the different layers during sintering; otherwise, a small amount of cracks will occur, affecting the mechanical properties of the product.

[0119] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a proton ceramic fuel cell, characterized in that: The proton ceramic fuel cell comprises: an oxygen ion conductor support layer; A transition layer, the transition layer being composited on the oxygen ion conductor support layer, the transition layer being prepared from cerium-based ceramic powder; an anode functional layer, the anode functional layer being made of a proton conductor material and being composited on the transition layer; an electrolyte layer, the electrolyte layer being composited on the anode functional layer; a cathode functional layer, the cathode functional layer being composited on the electrolyte layer; The cerium-based ceramic powder is CeO2, Ce 1-x Y x O2, Ce 1-x Zr x One of O2, where 0 <x<0.2; The thickness of the transition layer is 10 μm-100 μm; The preparation method comprises: Preparation of proton ceramic fuel half-cell green body; preparing a cathode functional layer membrane on one side of the electrolyte membrane of the proton ceramic fuel half-cell body to obtain a proton ceramic fuel cell body; The proton ceramic fuel cell body is sintered at a temperature of 1200° C. to 1600° C. for 10 hours to 20 hours and then cooled to obtain the proton ceramic fuel cell body; The oxygen ion conductor support layer is formed by mixing NiO powder and zirconium yttrium oxide powder, wherein the mass ratio of the NiO powder to the zirconium yttrium oxide powder is 1:(1-1.5); The transition layer is formed by mixing NiO powder and cerium-based ceramic powder, wherein the mass ratio of the NiO powder to the cerium-based ceramic powder is (2.5-3.5):1; The anode functional layer is formed by mixing NiO powder and proton conductor material powder, wherein the mass ratio of the NiO powder to the proton conductor material powder is (1.3-1.7):

1.

2. The preparation method according to claim 1, characterized in that The preparation of a proton ceramic fuel half-cell body includes: Weighing NiO powder and zirconium yttrium oxide powder, and pressing them under a pressure of not less than 50 MPa to form an oxygen ion conductor support layer membrane; Laying transition layer material powder on the oxygen ion conductor support layer membrane and pressing and molding it at a pressure of not less than 70 MPa to prepare a transition layer membrane; Laying anode functional layer material powder on the transition layer and pressing and molding it under a pressure of not less than 70 MPa to prepare an anode functional layer membrane; Electrolyte material powder is laid on the anode functional layer and pressed under a pressure of not less than 200 MPa to prepare an electrolyte layer membrane.

3. The preparation method according to claim 1, characterized in that The preparation of a proton ceramic fuel half-cell body includes: The oxygen ion conductor support layer membrane, transition layer membrane, anode functional layer membrane and electrolyte layer membrane are prepared by tape casting; The above membrane is subjected to a multi-step hot isostatic pressing process of "oxygen ion conductor support layer membrane|transition layer membrane|anode functional layer membrane|electrolyte layer membrane" to obtain the membrane.

4. The preparation method according to any one of claims 1 to 3, characterized in that The proton conductor material is BaZr 1-x-y Ce y Y x O 3−δ 、BaZr 1-x-y-z Ce z Y y Yb x O 3−δ One of the following, where 0 <x<1,0<y<1,0<z<1,0<δ<1。 5. A proton ceramic fuel cell comprising a transition layer, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 4.

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