An integrated structure composite conduction type solid oxide battery and preparation method thereof

Abstract

The present invention provides an integrated structure composite conduction type solid oxide battery and a preparation method thereof, belonging to the technical field of solid oxide fuel cells, including: an integrated framework, the integrated framework includes an electrolyte layer and porous layers on both sides, the integrated framework is composed of a proton conductor material and an oxygen ion conductor material, the molar ratio of the proton conductor material to the oxygen ion conductor material is 1:(0.8-1.2), and it is prepared by mixing and sintering a proton conductor material with an average particle size of 50-60 nm and an oxygen ion conductor material with an average particle size of 0.1-0.2 μm; a catalyst layer, the catalyst layer is located on the pore walls of the porous layers. By limiting the ratio and particle size of the proton conductor material and the oxygen ion conductor material, the present invention prepares more conductive paths and improves the output power of the solid oxide battery.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid oxide fuel cells, and particularly relates to an integrated structure composite conducting solid oxide cell and a preparation method thereof. Background Art

[0002] A solid oxide fuel cell (SOFC) is a clean energy conversion device that can directly convert chemical energy into electrical energy. According to the different ions conducted by the electrolyte material, SOFC can be divided into an oxygen ion conductor type (O-SOFC) and a proton conductor type (H-SOFC). Traditional high-temperature O-SOFCs have been developed for many years, with mature preparation technologies and excellent performance at high temperatures. However, as the operating conditions of the battery develop towards medium and low temperatures, proton conductor type SOFCs (H-SOFCs) have received extensive attention due to their lower operating temperatures, smaller activation energy values, and higher battery efficiencies. However, H-SOFCs are not yet fully developed, and the chemical stability and mechanical stability of proton conductor materials at high temperatures still need to be further improved to ensure no degradation during long-term operation.

[0003] In the prior art, a Chinese invention patent with the publication number CN109921079B discloses a composite solid oxide fuel cell and a preparation method thereof. The composite electrolyte layer has both proton conductivity and oxygen ion conductivity, and the electrolyte ion conductivity can meet the performance requirements at medium, low, and high temperatures. The composite porous electrolyte interlayer can effectively block the reaction between the cathode and the electrolyte, reducing the interfacial resistance. The double cathode layer is composed of an electron conductivity enhancement layer and an ion conductivity enhancement layer, greatly reducing the polarization resistance. A Chinese invention patent with the publication number CN114843569B discloses a preparation method, product, and battery of a proton-oxygen ion mixed conductor electrolyte. SDC is introduced into BZCYYb and evenly distributed to prepare a proton-dominated proton-oxygen ion mixed conductor electrolyte and anode, reducing the sintering temperature, and being able to conduct a small amount of oxygen ions to the anode and react to generate a certain amount of water vapor to realize in-situ humidification of the anode, ultimately reducing the production and operation costs. However, the above technical solutions have corresponding problems. Since a proton conductor material and an oxygen ion conductor material are used to prepare the electrolyte in a mixed manner, if the mixing uniformity is relatively high, similar to an amorphous structure, at this time, the proton conduction path and the oxygen ion conduction path in the electrolyte cannot connect both sides of the electrolyte, but will instead reduce the performance of the prepared solid oxide fuel cell; if the mixing degree is poor, a relatively large proportion of non-conducting paths will appear, which will also reduce the performance of the prepared solid oxide fuel cell. Summary of the Invention

[0004] In view of the above deficiencies in the prior art, the present invention provides an integrated structure composite conduction type solid oxide battery and a preparation method thereof. By limiting the ratio and particle size of the proton conductor material and the oxygen ion conductor material, more conductive paths are prepared to improve the output power of the solid oxide battery.

[0005] 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 an integrated structure composite conduction type solid oxide battery, including: an integrated framework, the integrated framework includes an electrolyte layer and porous layers on both sides, the integrated framework is composed of a proton conductor material and an oxygen ion conductor material, and the molar ratio of the proton conductor material to the oxygen ion conductor material is 1:(0.8 - 1.2), and it is prepared by mixing and sintering a proton conductor material with an average particle size of 50 - 60 nm and an oxygen ion conductor material with an average particle size of 0.1 - 0.2 μm; a catalyst layer, the catalyst layer is located on the pore walls of the porous layers.

[0007] Further, the electrolyte layer and the porous layers adopt the same proton conductor material and oxygen ion conductor material and have the same molar ratio.

[0008] Further, the proton conductor material includes: BaZr 1-x Y x O 3-δ 、BaZr 1-x Yb x O 3-δ 、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 or more of them, where 0 < x < 1, 0 < y < 1, 0 < z < 1, 0 < δ < 1.

[0009] Further, the oxygen ion conductor material includes: Zr x Y y O 2-δ 、Ce x Sm y O 2-δ ,Ce x Gd y O 2-δ 、La 1- x Sr x Ga 1-y Mg yO 3-δ One or more of them, where 0 < x < 1, 0 < y < 1, 0 < δ < 1.

[0010] On the other hand, the present invention provides a method for preparing the above-mentioned solid oxide battery, including: preparing an integrated framework; preparing a catalyst layer on the inner wall of the porous layer of the integrated framework.

[0011] Further, preparing the integrated framework includes: preparing an electrolyte membrane sheet and two electrode membrane sheets; using hot isostatic pressing to form according to "electrode membrane sheet|electrolyte membrane sheet|electrode membrane sheet" to obtain a green body of the integrated framework; sintering the green body of the integrated framework to obtain the integrated framework.

[0012] Further, the method for preparing the slurries of the electrolyte membrane sheet and the electrode membrane sheet is: weighing a proton conductor material and an oxygen ion conductor material according to a preset ratio and mixing them, adding a dispersant accounting for 8%-13% of the total powder mass, a plasticizer accounting for 3%-7% of the total powder mass, and a binder accounting for 9%-12% of the total powder mass, and mixing evenly to obtain the slurries.

[0013] Further, the dispersant is one or more of triethanolamine, sodium polyacrylate, and polyethylene oxide; the plasticizer and the binder are one or more of dioctyl phthalate, polyethylene glycol, polyvinyl alcohol, and polyvinyl acetate.

[0014] Further, the process of the hot isostatic pressing treatment is: maintaining at a pressure of 50-85°C and 10-60 MPa for at least 30 min.

[0015] Further, the sintering process is: heating at a rate not greater than 1°C / min to 650-700°C and holding for at least 30 min, heating at a rate not greater than 3°C / min to 1200-1600°C and holding for 2-20 h, and then cooling to room temperature at a rate not greater than 5°C / min.

[0016] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0017] (1) In this application, the average particle size and addition amount of the proton conductor material and the oxygen ion conductor material are defined. The average particle size and addition amount of the proton conductor material and the oxygen ion conductor material determine the distribution characteristics between the two. Specifically, the particle size of the proton conductor material is relatively small, which is suitable for the transfer of H ions. Moreover, due to the small particle size of the proton conductor material, it has a high surface free energy and strong adsorption ability, and can form certain agglomerates attached to the surface of the agglomerated mass formed by the oxygen ion conductor material, forming a path after sintering. However, the particle size of the proton conductor material should not be too small, otherwise it will agglomerate seriously by itself and cannot sinter to form an effective conduction path. The larger particle size of the oxygen ion conductor material is considered because the oxygen ion conductor material is not easy to form spherical agglomerates but forms irregularly shaped agglomerates, thereby increasing the probability of the oxygen ion conductor material penetrating the path on both sides of the electrolyte. Secondly, the formation of the above path is closely related to the ratio of the proton conductor material and the oxygen ion conductor material. Especially for the proton conductor material, if the molar ratio is small, it may not be able to form an effective conduction path, but instead lead to a power reduction; while if the molar ratio is high, the proportion of the oxygen ion conductor material decreases, resulting in the oxygen ion conductor material being prone to form spherical agglomerates and reducing the effective conduction path of the oxygen ion channel. Finally, the particle size and ratio of the above proton conductor material and oxygen ion conductor material can reduce the probability of cracks caused by different thermal physical properties between the two. Since the integrated framework is prepared from two materials and the selection range of the two materials is relatively large, it is necessary to consider the thermal physical property differences between different materials. By defining the particle size and ratio of the proton conductor material and the oxygen ion conductor material in this application, the influence of thermal physical property differences on the prepared integrated framework can be ignored.

[0018] (2) The overall framework area of the integrated structure proton-oxygen ion composite conduction type solid oxide battery realizes the integration of two fuel cells with oxygen ion conduction mode and proton conduction mode. The ion transport channel range is wider. This integration significantly improves the working efficiency and adaptability of the fuel cell, enables the battery to operate efficiently within a wider temperature range, makes full use of the advantages under different working conditions, and achieves higher fuel utilization efficiency.

[0019] (3) The composite conductor material is composed of a proton conductor material with a nanoscale particle size and an oxygen ion conductor material with a micron-scale particle size, and 1% mass fraction of NiO is added as a sintering aid in the proton conductor material. By using material particles with different particle sizes, the sintering performance of the material is significantly improved, and the mechanical strength and durability of the material are enhanced to a certain extent.

[0020] (4) The main framework support structure of the integrated structure proton-oxygen ion composite conduction type solid oxide battery is an integral whole: This integral structure ensures the tight combination of the electrode and the electrolyte layer, effectively avoids the separation problems that may occur during operation, and enhances the stability and durability of the battery.

[0021] (5) Construct a nanostructured electrode by impregnating the electrode material onto the surface of the porous skeleton: The nanostructured electrode is located on the surface of the skeleton, significantly increasing the reactive active sites without occupying the composite conductor region, and improving the connectivity of each phase in the skeleton. This not only maintains the high activity of the catalyst, increases the electrode reaction rate, but also ensures that the composite conductor ceramic skeleton has good proton and oxygen ion conduction capabilities, further enhancing the overall performance of the fuel cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0023] Figure 1 Schematic diagram of the solid oxide battery provided by the embodiment of the present invention;

[0024] Figure 2 Schematic diagram of the non-conducting path of the solid oxide battery provided by the embodiment of the present invention;

[0025] Figure 3 SEM image of the solid oxide battery provided by Embodiment 1 of the present invention;

[0026] Figure 4 Partial enlarged view of the solid oxide battery provided by Embodiment 1 of the present invention.

[0027] Reference numerals: 1, oxygen electrode catalyst layer; 2, integrated skeleton; 3, fuel electrode catalyst layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0028] To make the objectives, technical solutions, and advantages of the present invention clearer, the following will further elaborate on the present invention in conjunction with the drawings and specific embodiments. The specific embodiments of the present invention are not limited to the specific embodiments given here. Those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the disclosed specific embodiments.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs. The terms used are only for describing specific embodiments and do not limit the present invention.

[0030] The embodiment of the present invention provides an integrated structure composite conduction type solid oxide battery, as Figure 1As shown in the figure, it includes: an integrated framework 2, the integrated framework 2 includes an electrolyte layer and porous layers on both sides, the integrated framework 2 is composed of a proton conductor material and an oxygen ion conductor material, and the molar ratio of the proton conductor material to the oxygen ion conductor material is 1:(0.8 - 1.2), and it is prepared by mixing and sintering a proton conductor material with an average particle size of 50 - 60 nm and an oxygen ion conductor material with an average particle size of 0.1 - 0.2 μm; a catalyst layer, the catalyst layer is located on the pore walls of the porous layers. As Figure 1 shown in the figure, the catalyst layer includes an oxygen electrode catalyst layer 1 and a fuel electrode catalyst layer 3.

[0031] In the prior art, as Figure 2 shown in the figure, the composite conduction type integrated framework includes a proton conductor material and an oxygen ion conductor material. The proton conductor material is used to transport protons, and the oxygen ion conductor material is used to transport oxygen ions. The prepared integrated framework inevitably has non-conductive paths. The non-conductive paths reduce the proton or oxygen ion transport interface area, resulting in low power. To solve the above problems, the present application limits the average particle size and addition amount of the proton conductor material and the oxygen ion conductor material. The average particle size and addition amount of the proton conductor material and the oxygen ion conductor material determine the distribution characteristics between the two. Specifically, the particle size of the proton conductor material is relatively small, which is suitable for the transfer of H ions. And because the particle size of the proton conductor material is small, the surface free energy is high, and it has strong adsorption ability, and can form certain aggregates attached to the surface of the agglomerated blocks formed by the oxygen ion conductor material, and form a path after sintering. However, the particle size of the proton conductor material should not be too small, otherwise its own agglomeration is serious and it cannot sinter to form an effective conductive path; the larger particle size of the oxygen ion conductor material is considered because the oxygen ion conductor material is not suitable for forming spherical aggregates, but forms irregular aggregates, so as to increase the probability of the oxygen ion conductor material penetrating the paths on both sides of the electrolyte; secondly, the formation of the above paths is closely related to the ratio of the proton conductor material and the oxygen ion conductor material, especially the proton conductor material. If the molar ratio is small, it may not be able to form an effective conductive path, but instead lead to a power reduction; while if the molar ratio is high, the proportion of the oxygen ion conductor material decreases, resulting in the oxygen ion conductor material being prone to form spherical aggregates, reducing the effective conductive paths of the oxygen ion channels; finally, the particle size and ratio of the above proton conductor material and oxygen ion conductor material can reduce the probability of cracks caused by different thermal physical properties between the two. Since the integrated framework is prepared from two materials and the selection range of the two materials is large, it is necessary to consider the thermal physical property differences between different materials. The present application can ignore the influence of thermal physical property differences on the prepared integrated framework by limiting the particle size and ratio of the proton conductor material and the oxygen ion conductor material.

[0032] Specifically, the electrolyte layer and the porous layer are made of the same proton conductor material and oxygen ion conductor material, and the molar ratios of the two are the same. This is to improve the coordination between the electrolyte layer and the porous layer during heating and cooling processes, and to avoid stress at the interface between the porous layer and the electrolyte layer due to different thermal properties. When the stress is greater than the local maximum allowable stress, cracks will appear, resulting in performance degradation of the solid oxide battery.

[0033] Specifically, the proton conductor material includes: BaZr 1-x Y x O 3-δ 、BaZr 1-x Yb x 、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 or more of them, where 0 < x < 1, 0 < y < 1, 0 < z < 1, 0 < δ < 1.

[0034] Specifically, the oxygen ion conductor material includes: ZrO 2-x Y2O 3-δ 、Ce x Sm y O 2-δ 、Ce x Gd y O 2-δ 、La 1- x Sr x Ga 1-y Mg y O 3-δ One or more of them, where 0 < x < 1, 0 < y < 1, 0 < δ < 1.

[0035] Specifically, the oxygen electrode catalyst layer is composed of an electronic conductor or an ionic and electronic mixed conductor. The specific materials include: Pr6O 11 、Ce 1-x Pr x O2、PrNi 1-x Co x O 3-δ 、Ba 1-x Sr x Co y Fe 1-y O 3-δ 、La 1-x Sr x Co y Fe 1-y O3-δ 、 BaCo y Fe 1-x-y-z Zr x Y z O 3-δ One or more of them, where 0 < x < 1, 0 < y < 1, 0 < z < 1, 0 < δ < 1.

[0036] Specifically, the fuel electrode catalyst layer is composed of a metal or a metal-ceramic composite material or an electron-ion mixed conductor. Specific materials include: Ni, NiFe, Ni / Ce 1-x Gd x O 2-δ 、 Ni / Sm 1-x Ce x O 2-δ 、 Sr2Fe 2-x Mo x O 6-δ One or more of them, where 0 < x < 1, 0 < δ < 1.

[0037] For illustration purposes, in the subsequent examples, the proton conductor materials used are BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ and BaZr 0.7 Ce 0.1 Y 0.1 Yb 0.1 O 3-δ , the oxygen ion conductor materials used are GDC and SDC, where GDC is CeO2 stabilized by 40% molar composition of Gd2O3, and SDC is Sm 0.2 Ce 0.8 O2, the fuel electrode catalyst used is Ni / SDC, and the oxygen electrode catalyst used is PrNi 0.5 Co 0.5 O 3-δ or La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ .

[0038] For the solid oxide battery prepared by the present invention, the porosity on the oxygen electrode side is 10%-60%, the density of the composite conductor electrolyte layer structure is not less than 95%, and the porosity on the fuel electrode side is 10%-60%. In the embodiments of the present invention, the thickness of the integrated structure with proton-oxygen ion composite conduction is 200-1500 μm. Among them, according to different support structures, these structures can be further divided into electrolyte-supported type and electrode-supported type. The thickness of the oxygen electrode is 10-50 μm, the thickness of the composite conductor electrolyte layer is 10-700 μm, and the thickness of the fuel electrode is 10-700 μm. The thickness of the prepared fuel electrode catalyst layer and oxygen electrode catalyst layer is 50-200 nm.

[0039] The embodiments of the present invention also provide a preparation method for the above solid oxide battery, including:

[0040] S1. Prepare an integrated framework.

[0041] Preparing the integrated framework includes:

[0042] S10. Prepare an electrolyte membrane sheet and two electrode membrane sheets;

[0043] The preparation method for the slurries of the electrolyte membrane sheet and the electrode membrane sheets is as follows:

[0044] Weigh the proton conductor material and the oxygen ion conductor material according to a preset ratio and mix them. Then add a dispersant accounting for 8%-13% of the total powder mass, a plasticizer accounting for 3%-7% of the total powder mass, and a binder accounting for 9%-12% of the total powder mass, and mix them evenly to obtain the slurries. As the second technical difficulty of this application, how to ensure that the slurries prepared from the proton conductor material or the oxygen ion conductor material have a certain degree of dispersibility and a certain degree of agglomeration. The reason for maintaining a certain degree of dispersibility is that on the one hand, it can avoid large-area agglomeration between powders, which may cause cracks due to large differences in thermal properties during the preparation process of the integrated framework. On the other hand, if the dispersibility is too high, a similar amorphous structure will appear, and an effective conduction path cannot be formed, which will instead reduce the power of the solid oxide battery. Therefore, it is necessary to limit the contents of the dispersant, plasticizer, and binder to ensure that the prepared slurries have appropriate dispersibility and agglomeration, so as to prepare an integrated framework with many conduction paths.

[0045] Specifically, the dispersant uses one or more of triethanolamine, sodium polyacrylate, and polyethylene oxide; the plasticizer and the binder use one or more of dioctyl phthalate, polyethylene glycol, polyvinyl alcohol, and polyvinyl acetate. The above products are all commercially available products. Since the plasticizer can usually also be used as a binder, the plasticizer and the binder can be selected from the same or different substances among the above substances.

[0046] Sodium polyacrylate was purchased from Zhonglianbang, model K-334; polyethylene oxide was of the WSR N-10NF grade; polyethylene glycol was polyethylene glycol 1500; polyvinyl alcohol was polyvinyl alcohol 1750±50; polyvinyl acetate was purchased from Thermo Fisher, catalog number 18326.

[0047] The preparation methods of the electrolyte membrane and the electrode membrane include: one or more of the casting method, the screen printing method, the spin coating method, and the spraying method. For illustration purposes, the subsequent examples will be described using the casting method.

[0048] It should be noted that the above mixing or blending is all carried out by ball milling, and the ball milling time is not less than 36 h.

[0049] S11 uses hot isostatic pressing to form according to "electrode membrane|electrolyte membrane|electrode membrane" to obtain an integrated skeleton green body.

[0050] The process of the hot isostatic pressing treatment is: at a temperature of 50 - 85 °C and a pressure of 10 - 60 MPa, hold for at least 30 min. Multi-step hot isostatic pressing is to add different membranes layer by layer and carry out hot isostatic pressing forming. For example, first, the fuel electrode membrane and the electrolyte membrane are subjected to hot isostatic pressing treatment. After completion, the oxygen electrode membrane is stacked on the other side of the electrolyte membrane and hot isostatic pressing treatment is carried out. After the hot isostatic pressing treatment, an integrated skeleton green body is obtained.

[0051] S12 sinter the integrated skeleton green body to obtain the integrated skeleton.

[0052] The sintering process is: raise the temperature to 650 - 700 °C at a rate not greater than 1 °C / min and hold for at least 30 min, then raise the temperature to 1200 - 1600 °C at a rate not greater than 3 °C / min and hold for 2 - 20 h, and then cool to room temperature at a rate not greater than 5 °C / min. The sintering process of this application fully considers the different thermal physical properties of the proton conductor material and the oxygen ion conductor material, and avoids cracks between the two phases during the sintering process.

[0053] S2. Prepare a catalyst layer on the inner wall of the porous layer of the integrated skeleton.

[0054] To prepare a catalyst layer on the inner wall of the porous layer of the integrated skeleton, the catalyst layer can be prepared by the impregnation method or the hydrothermal reaction. In the embodiments of the present invention, the impregnation method is preferably used to prepare the catalyst layer, and then high-temperature sintering is used to prepare a solid oxide battery.

[0055] The process of the high-temperature sintering is: sinter at a temperature of 700 - 1000 °C for 1.5 - 3.0 h.

[0056] The working conditions for testing the battery performance in the embodiments of the present invention are as follows: using high-purity H2 as the fuel gas with a flow rate of 75 mL / min, air as the oxidant with a flow rate of 150 mL / min, and measuring the open-circuit voltage and power at 500 °C.

[0057] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0058] Embodiment 1

[0059] A preparation method of a solid oxide battery provided in this embodiment, and a solid oxide battery prepared by using this preparation method, include:

[0060] S1. Prepare an integrated framework.

[0061] In the BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ powder, add 1% by mass of NiO sintering aid, after ball milling and mixing evenly, then mix with GDC powder in a molar ratio of 1:1. The average particle size of the BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ powder is 50 nm, and the average particle size of the GDC powder is 0.1 μm. Add 10% of the total powder mass of triethanolamine, 5% of the total powder mass of dioctyl phthalate, and 10% of the total powder mass of polyethylene glycol to make an electrolyte casting slurry, add zirconia milling beads for ball milling for 36 h to obtain the electrolyte casting slurry; use the same method and materials to prepare an electrode framework casting slurry containing 40% pore-forming agent; use a membrane tape casting machine to prepare two-electrode membrane sheets and electrolyte casting membrane sheets; use hot isostatic pressing to form according to "electrode membrane sheet|electrolyte membrane sheet|electrode membrane sheet" to obtain an integrated framework green body; sinter the integrated framework green body, and the sintering process is: rise to 650 °C at a rate of 0.5 °C / min and hold for 30 min, rise to 1400 °C at a rate of 3 °C / min and hold for 10 h, and then cool to room temperature at a rate of 3 °C / min to obtain the integrated framework.

[0062] S2. Prepare a catalyst layer on the inner wall of the porous layer of the integrated framework.

[0063] Mix metal nitrates Pr(NO3)3, Ni(NO3)3, and Co(NO3)2 according to a molar ratio of Pr:Ni:Co = 2:1:1, and then add 10% of the total mass of the added Pr, Ni, and Co elements of surfactant, and add a certain amount of water to prepare a PNC oxygen electrode impregnation solution with a concentration of 0.7 mol / L.

[0064] Mix the metal nitrate solutions according to the molar ratio of Ni:Sm:Ce = 5:1:4, then add a surfactant according to 10% of the total mass of Ni, Sm, and Ce elements, and add a certain amount of water to prepare a Ni / SDC fuel electrode impregnation solution with a concentration of 0.7 mol / L.

[0065] Absorb the above impregnation solution and drop it into the electrode skeletons of the corresponding functional areas respectively, put it into a muffle furnace for debinding treatment, repeat the above operations multiple times until the solution cannot penetrate, and finally perform sintering to obtain a complete solid oxide battery. The sintering process is: sinter at a temperature of 800 °C for 2 h. The prepared solid oxide battery is as Figure 3 shown.

[0066] From Figure 4 it can be seen that the solid oxide battery prepared in this application has more conductive paths and no cracks are found. By measurement, the open-circuit voltage is 1.005 V, and the power can reach 601 mW·cm -2 .

[0067] Example 2

[0068] A method for preparing a solid oxide battery provided in this example, and a solid oxide battery prepared by using this preparation method, include:

[0069] S1. Prepare an integrated skeleton.

[0070] Add a NiO sintering aid with a mass fraction of 1% to the BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ powder, mix evenly by ball milling, and then mix with GDC powder according to a molar ratio of 1:0.8. The BaZr 0.7 Ce 0.2 Y 0.1 O 3-δThe average particle size of the powder is 55 nm, and the average particle size of the GDC powder is 0.13 μm. Triethanolamine accounting for 8% of the total powder mass, dioctyl phthalate accounting for 3% of the total powder mass, and polyethylene glycol accounting for 9% of the total powder mass are added to prepare an electrolyte tape-casting slurry. Zirconia milling beads are added for ball milling for 36 h to obtain the electrolyte tape-casting slurry; the electrode skeleton tape-casting slurry containing 40% pore former is prepared using the same method and materials; a two-electrode membrane sheet and an electrolyte tape-casting membrane sheet are obtained by using a film tape-casting machine; hot isostatic pressing is used to form in the order of "electrode membrane sheet|electrolyte membrane sheet|electrode membrane sheet" to obtain an integrated skeleton green body; the integrated skeleton green body is sintered, and the sintering process is as follows: heating to 700 °C at a rate of 1 °C / min and holding for 30 min, heating to 1200 °C at a rate of 3 °C / min and holding for 2 h, and then cooling to room temperature at a rate of 5 °C / min to obtain the integrated skeleton.

[0071] S2. Prepare a catalyst layer on the inner wall of the porous layer of the integrated skeleton.

[0072] According to the molar ratio of Pr:Ni:Co = 2:1:1, the metal nitrates Pr(NO3)3, Ni(NO3)3, and Co(NO3)2 are mixed, and a surfactant is added according to 10% of the total mass of the added Pr, Ni, and Co elements, and a certain amount of water is added to prepare a PNC oxygen electrode impregnation solution with a concentration of 0.7 mol / L.

[0073] According to the molar ratio of Ni:Sm:Ce = 5:1:4, their metal nitrate solutions are mixed, and a surfactant is added according to 10% of the total mass of the Ni, Sm, and Ce elements, and a certain amount of water is added to prepare a Ni / SDC fuel electrode impregnation solution with a concentration of 0.7 mol / L.

[0074] The above impregnation solution is sucked and dropped into the electrode skeleton of the corresponding functional area, and then placed in a muffle furnace for debinding treatment. The above operation is repeated multiple times until the solution cannot penetrate, and finally sintering is carried out to obtain a complete solid oxide battery. The sintering process is as follows: sintering at a temperature of 700 °C for 1.5 h.

[0075] The solid oxide battery prepared in this application has more conductive paths and no cracks are found; through measurement, the open-circuit voltage of the prepared solid oxide battery is 1.001 V, and the power can reach 588 mW·cm -2 。

[0076] Example 3

[0077] A method for preparing a solid oxide battery provided in this embodiment, and a solid oxide battery prepared by using this preparation method, include:

[0078] S1. Prepare an integrated skeleton.

[0079] In BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ powder, 1% by mass of NiO sintering aid is added. After ball milling and mixing evenly, it is then mixed with GDC powder at a molar ratio of 1:1.2. The average particle size of the BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ powder is 60 nm, and the average particle size of the GDC powder is 0.2 μm. Triethanolamine accounting for 13% of the total powder mass, dioctyl phthalate accounting for 7% of the total powder mass, and polyethylene glycol accounting for 12% of the total powder mass are added to make an electrolyte tape-casting slurry. Zirconia milling beads are added for ball milling for 36 h to obtain the electrolyte tape-casting slurry; The electrode skeleton tape-casting slurry containing 40% pore former is prepared using the same method and materials; Two-electrode membrane sheets and electrolyte tape-casting membrane sheets are obtained by using a film-tape casting machine; Hot isostatic pressing is used to form according to "electrode membrane sheet|electrolyte membrane sheet|electrode membrane sheet" to obtain an integrated skeleton green body; The integrated skeleton green body is sintered, and the sintering process is: heating to 650 °C at a rate of 0.5 °C / min and holding for 1 h, heating to 1600 °C at a rate of 3 °C / min and holding for 20 h, and then cooling to room temperature at a rate of 5 °C / min to obtain the integrated skeleton.

[0080] S2. Prepare a catalyst layer on the inner wall of the porous layer of the integrated skeleton.

[0081] According to the molar ratio of Pr:Ni:Co = 2:1:1, metal nitrates Pr(NO3)3, Ni(NO3)3, and Co(NO3)2 are mixed, and then 10% of the total mass of the added Pr, Ni, and Co elements is added with a surfactant, and a certain amount of water is added to prepare a PNC oxygen electrode impregnation solution with a concentration of 0.7 mol / L.

[0082] According to the molar ratio of Ni:Sm:Ce = 5:1:4, their metal nitrate solutions are mixed, and then 10% of the total mass of the Ni, Sm, and Ce elements is added with a surfactant, and a certain amount of water is added to prepare a Ni / SDC fuel electrode impregnation solution with a concentration of 0.7 mol / L.

[0083] The above impregnation solutions are respectively sucked and dropped into the electrode skeletons of the corresponding functional areas, and then placed in a muffle furnace for debinding treatment. The above operations are repeated multiple times until the solution cannot penetrate, and finally sintering is carried out to obtain a complete solid oxide battery. The sintering process is: sintering at a temperature of 1000 °C for 3 h.

[0084] The solid oxide battery prepared in this application has more conductive paths and no cracks are found. Through measurement, the open-circuit voltage of the prepared solid oxide battery is 1.003 V, and the power can reach 594 mW·cm -2 。

[0085] Example 4

[0086] A method for preparing a solid oxide battery provided in this example, and a solid oxide battery prepared by using this preparation method, include:

[0087] S1. Prepare an integrated skeleton.

[0088] In BaZr 0.7 Ce 0.1 Y 0.1 Yb 0.1 O 3-δ powder, add 1% by mass of NiO sintering aid, after ball milling and mixing evenly, then mix with SDC powder at a molar ratio of 1:1. The average particle size of the BaZr 0.7 Ce 0.1 Y 0.1 Yb 0.1 O 3-δ powder is 50 nm, and the average particle size of the SDC powder is 0.1 μm. Add 10% of the total powder mass of triethanolamine, 5% of the total powder mass of dioctyl phthalate, and 10% of the total powder mass of polyethylene glycol to make an electrolyte tape-casting slurry, add zirconia ball milling beads and ball mill for 36 h to obtain the electrolyte tape-casting slurry; use the same method and materials to prepare an electrode skeleton tape-casting slurry containing 40% pore former; use a film-tape casting machine to prepare two-electrode membrane sheets and electrolyte tape-casting membrane sheets; use hot isostatic pressing to form according to "electrode membrane sheet|electrolyte membrane sheet|electrode membrane sheet" to obtain an integrated skeleton green body; sinter the integrated skeleton green body, and the sintering process is: heat up to 700 °C at 0.5 °C / min and hold for 2 h, heat up to 1400 °C at 3 °C / min and hold for 10 h, and then cool to room temperature at 3 °C / min to obtain the integrated skeleton.

[0089] S2. Prepare a catalyst layer on the inner wall of the porous layer of the integrated skeleton.

[0090] Mix metal nitrates La(NO3)3, Sr(NO3)3, Co(NO3)2, and Fe(NO3)2 according to a molar ratio of La:Sr:Co:Fe = 3:2:1:4, and then add 10% of the total mass of the added La, Sr, Co, and Fe elements of the surfactant P123, and add a certain amount of water to prepare an LSCF oxygen electrode impregnation solution with a concentration of 0.7 mol / L.

[0091] Mix the metal nitrate solutions according to the molar ratio of Ni:Sm:Ce = 5:1:4, add a surfactant according to 10% of the total mass of Ni, Sm, and Ce elements, and add a certain amount of water to prepare a Ni / SDC fuel electrode impregnation solution with a concentration of 0.7 mol / L.

[0092] Absorb the above impregnation solution and drop it into the electrode skeletons of the corresponding functional areas, put it into a muffle furnace for debinding treatment, repeat the above operations multiple times until the solution cannot penetrate, and finally sinter to obtain a complete solid oxide battery. The sintering process is: sinter at a temperature of 900 °C for 2 h.

[0093] The solid oxide battery prepared in this application has more conductive paths and no cracks are found; through measurement, the open-circuit voltage of the prepared solid oxide battery is 0.999 V, and the power can reach 579 mW·cm -2 。

[0094] Comparative Example 1

[0095] Compared with Example 1, the difference is that in step S1, the average particle size of the BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ powder is 45 nm.

[0096] Through measurement, the open-circuit voltage of the prepared solid oxide battery is 0.850 V, and the power can reach 422 mW·cm -2 。

[0097] Comparative Example 2

[0098] Compared with Example 1, the difference is that in step S1, the average particle size of the BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ powder is 45 nm.

[0099] Through measurement, the open-circuit voltage of the prepared solid oxide battery is 0.848 V, and the power can reach 410 mW·cm -2 。

[0100] Comparative Example 3

[0101] Compared with Example 1, the difference is that in step S1, the average particle size of the GDC powder is 0.08 μm.

[0102] Through measurement, the open-circuit voltage of the prepared solid oxide battery is 0.830 V, and the power can reach 385 mW·cm -2 。

[0103] Comparative Example 4

[0104] Compared with Example 1, the difference lies in that in step S1, the average particle size of the GDC powder is 0.23 μm.

[0105] By measurement, the open-circuit voltage of the prepared solid oxide battery is 0.721 V, and the power can reach 320 mW·cm -2 。

[0106] Comparative Example 5

[0107] Compared with Example 1, the difference lies in that in step S1, BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ The average particle size of the powder is 45 nm, and the average particle size of the GDC powder is 0.23 μm.

[0108] By measurement, the open-circuit voltage of the prepared solid oxide battery is 0.712 V, and the power can reach 297 mW·cm -2 。

[0109] Comparative Example 6

[0110] Compared with Example 1, the difference lies in that in step S1, triethanolamine accounting for 7% of the total powder mass, dioctyl phthalate accounting for 3% of the total powder mass, and polyethylene glycol accounting for 9% of the total powder mass are added to prepare the electrolyte tape-casting slurry.

[0111] By measurement, the open-circuit voltage of the prepared solid oxide battery is 0.846 V, and the power can reach 401 mW·cm -2 。

[0112] Comparative Example 7

[0113] Compared with Example 1, the difference lies in that in step S1, triethanolamine accounting for 14% of the total powder mass, dioctyl phthalate accounting for 3% of the total powder mass, and polyethylene glycol accounting for 9% of the total powder mass are added to prepare the electrolyte tape-casting slurry.

[0114] By measurement, the open-circuit voltage of the prepared solid oxide battery is 0.856 V, and the power can reach 430 mW·cm -2 。

[0115] Comparative Example 8

[0116] Compared with Example 1, the difference lies in that in step S1, triethanolamine accounting for 10% of the total powder mass, dioctyl phthalate accounting for 2% of the total powder mass, and polyethylene glycol accounting for 10% of the total powder mass are added to prepare the electrolyte tape-casting slurry.

[0117] By measurement, the open-circuit voltage of the prepared solid oxide battery is 0.795 V, and the power can reach 372 mW·cm -2 .

[0118] Comparative Example 9

[0119] Compared with Example 1, the difference lies in that in step S1, triethanolamine accounting for 10% of the total powder mass, dioctyl phthalate accounting for 5% of the total powder mass, and polyethylene glycol accounting for 8% of the total powder mass are added to prepare the electrolyte casting slurry.

[0120] By measurement, the open-circuit voltage of the prepared solid oxide battery is 0.810 V, and the power can reach 380 mW·cm -2 .

[0121] From Example 1 and Comparative Examples 1-5, it can be seen that the molar ratio and particle size of the proton conductor material and the oxygen ion conductor material have a great influence on the final performance of the product. The reason is that a non-conducting type path is formed, resulting in a decrease in power and a decrease in open-circuit voltage. In addition to the above reasons, it also includes the thermal physical property mismatch between the proton conductor material and the oxygen ion conductor material, which superimposes the above factors and causes cracks between the two. From Example 1 and Comparative Examples 6-9, it can be seen that the proportion addition of the dispersant, plasticizer and binder is very crucial. Although the three belong to different functions, there is a certain influence between them. If the dispersant is more, the dispersion effect is good, and the oxygen ion conductor material and the proton conductor material form a similar amorphous structure, resulting in a decrease in voltage and a decrease in output power. If the dispersant is added less, the degree of segregation intensifies, resulting in an increase in non-conducting type paths, thereby causing a decrease in open-circuit voltage and a decrease in output power.

[0122] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An integrated structure composite conductive solid oxide battery, characterized in that: include: An integrated skeleton, wherein the integrated skeleton is composed of an electrolyte layer and porous layers on both sides, and the integrated skeleton is composed of a proton conductor material and an oxygen ion conductor material, wherein the molar ratio of the proton conductor material to the oxygen ion conductor material is 1:(0.8-1.2), the average particle size of the proton conductor material is 50-60 nm, and the average particle size of the oxygen ion conductor material is 0.1-0.2 μm; A catalyst layer, the catalyst layer comprising an oxygen electrode catalyst layer and a fuel electrode catalyst layer, the catalyst layer being located on a pore wall of the porous layer; The preparation of the integrated skeleton includes: preparing an electrolyte membrane and two electrode membranes; Hot isostatic pressing is used to form "electrode membrane|electrolyte membrane|electrode membrane" to obtain an integrated skeleton green body; Sintering the integrated skeleton green body to obtain the integrated skeleton; The preparation method of the electrolyte membrane slurry of the integrated skeleton is as follows: weigh the proton conductor material and the oxygen ion conductor material according to a preset ratio and mix them, add 8%-13% of the total powder mass of a dispersant, 3%-7% of the total powder mass of a plasticizer and 9%-12% of the total powder mass of a binder and mix them evenly; The preparation method of the electrode membrane slurry of the integrated skeleton is as follows: weigh and mix the proton conductor material and the oxygen ion conductor material according to a preset ratio, add 8%-13% of the total powder mass of a dispersant, 3%-7% of the total powder mass of a plasticizer, 9%-12% of the total powder mass of a binder and a pore-forming agent, and mix well to obtain the slurry.

2. The integrated structure composite conductive solid oxide battery according to claim 1, characterized in that: The electrolyte layer and the porous layer use the same proton conductor material and oxygen ion conductor material and the molar ratio of the two is the same.

3. The integrated structure composite conductive solid oxide battery according to claim 1, characterized in that: The proton conductor material includes: BaZr 1-x Y x O 3−δ 、BaZr 1-x Yb x O 3−δ 、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 or more of, where 0 <x<1,0<y<1,0<z<1,0<δ<1。 4. The integrated structure composite conductive solid oxide battery according to claim 1, characterized in that: The oxygen ion conductor material includes: Zr x Y y O 2−δ 、Ce x Sm y O 2−δ 、Ce x G y O 2−δ ,La 1-x Sr x Ga 1-y Mg y O 3−δ One or more of, where 0 <x<1,0<y<1,0<δ<1。 5. The method for preparing a solid oxide battery according to any one of claims 1 to 4, characterized in that: preparing an integrated skeleton; A catalyst layer is prepared on the inner wall of the porous layer of the integrated skeleton.

6. The preparation method according to claim 5, characterized in that: The dispersant is one or more of triethanolamine, sodium polyacrylate and polyoxyethylene; The plasticizer and the binder are one or more of dioctyl phthalate, polyethylene glycol, polyvinyl alcohol and polyvinyl acetate.

7. The preparation method according to claim 5, characterized in that: The hot isostatic pressing process is: maintaining the temperature at 50-85° C. and a pressure of 10-60 MPa for at least 30 minutes.

8. The preparation method according to claim 5, characterized in that: The sintering process is: heating to 650-700°C at a rate of no more than 1°C / min and keeping the temperature for at least 30 minutes, heating to 1200-1600°C at a rate of no more than 3°C / min and keeping the temperature for 2-20 hours, and then cooling to room temperature at a rate of no more than 5°C / min.

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