CN113258111A - Zirconium-based anode-supported solid oxide battery without isolation layer - Google Patents

Zirconium-based anode-supported solid oxide battery without isolation layer Download PDF

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CN113258111A
CN113258111A CN202110733733.6A CN202110733733A CN113258111A CN 113258111 A CN113258111 A CN 113258111A CN 202110733733 A CN202110733733 A CN 202110733733A CN 113258111 A CN113258111 A CN 113258111A
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layer
anode
electrolyte
membrane
nitrate
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CN113258111B (en
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郑紫微
雷泽
景俊萌
杨志宾
彭苏萍
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China University of Mining and Technology Beijing CUMTB
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a zirconium-based anode-supported solid oxide battery without an isolation layer, which is characterized by sequentially comprising an anode layer, an electrolyte layer and a membrane-coated cathode layer; wherein the anode layer is made of NiO and zirconium-based electrolyte mixed material, and the electrolyte layer is made of zirconium-based electrolyte material; the membrane-coated cathode layer consists of a membrane-coated functional layer and a membrane-coated current collecting layer, the membrane is a full-nano membrane with the thickness of 5-30nm, the membrane is a Sr-based perovskite material or metal oxide, and a nano membrane-coated structure is formed on the surface of the cathode layer by dipping the cathode layer in a precursor mixed solution of the coating material and calcining. According to the zirconium-based anode support solid oxide battery, the cerium oxide isolation layer is removed between the electrolyte layer and the cathode layer, so that the one-step high-temperature sintering process is reduced; the microstructure of the cathode material is optimized, the reaction between the cathode and the electrolyte is avoided, and the stability of the battery is improved.

Description

Zirconium-based anode-supported solid oxide battery without isolation layer
Technical Field
The invention relates to an intermediate-temperature solid oxide battery, in particular to a zirconium-based anode-supported solid oxide battery without an isolation layer and a preparation method thereof.
Background
The Solid Oxide Cell (SOC) is a high-efficiency all-solid-state energy conversion device, comprises a fuel cell mode (SOFC) and an electrolytic cell mode (SOEC), can realize direct mutual conversion between chemical energy and electric energy, and has the advantages of high energy conversion efficiency, no pollution in the reaction process, environmental friendliness and the like.
ZrO doped with different rare earth metal materials2The electrolyte material is the most widely applied electrolyte material at present, and the worldwide commercialized SOFC mostly takes the material as the electrolyte. However, doped ZrO2The material has poor chemical compatibility with the Sr-containing perovskite cathode material applied at medium and low temperature, and non-conductive SrZrO is generated at the interface between the electrolyte and the cathode by high-temperature calcination (1200-1400 ℃) during the preparation of the cathode3Secondary phases, affecting battery life; under the working condition of the battery (750 ℃), Sr element segregation is promoted in long-term discharge operation, and SrZrO is generated at the interface between the battery and a cathode3Affecting the stability of the battery.
The document reports that the SOFC battery without the isolation layer has fast performance attenuation, and the addition of the isolation layer can prevent Sr segregation and prolong the service life of the battery. Therefore, the common method at present is to add densely doped CeO at the interface of the electrolyte and the cathode2The isolation layer blocks Sr element segregation, prevents secondary phase generation and prolongs the service life of the battery. Due to doped CeO2The barrier layer is required to be thin (3-5 microns) and dense, with a densification temperature above 1450 deg.C and with doped ZrO2The electrolyte reacts at the temperature of more than 1400 ℃ to generate an insulating phase to reduce the performance of the battery, so that the sintering densification of the film prepared by simple and economic processes such as screen printing, spraying and the like at the reaction temperature (more than 1300 ℃) is difficult. The compact film below several microns can be prepared by applying special processes such as magnetron sputtering, pulsed laser deposition and the like, but the processes greatly increase the difficulty and cost of battery preparation.
CN 105226294B discloses a solid oxide fuel cell cathode material, its preparation and application: the cathode material is perovskite oxide A1 y1-A2 y BO3-δAnd tetravalent oxide MO modified on the surface of the perovskite oxide2To form the composite cathode. However, when Sr element is contained in a1 or a2 in the cathode material, in order to prevent Sr element segregation when applied to a zirconium-based electrolyte SOFC, it is still necessary to prepare a cerium-based separation layer between the cathode and the electrolyte, and there is a drawback that Sr segregation causes a reduction in battery life.
CN 111146456A adopts Gd z Ce z1-O2To La x Sr x1-Co y Fe y1-O3-δModifying to prepare the ion-conducting enhanced composite cathode material; wherein the content of the first and second substances,zis in the range of 0 to 1,xis in the range of 0 to 1, y is 0 to 1. But modified GdzCe1-zO2After the battery runs for a long time, the particle size grows, Sr segregation cannot be blocked, and finally the battery performance is greatly attenuated, and the service life of the battery is shortened.
CN 111584890A discloses an in-situ self-stabilization type solid oxide fuel cell cathode, which is characterized in that the cathode comprises an active material with a core-shell structure, and a core body is La0.6Sr0.4Co0.2Fe0.8O3-δThe shell layer is a perovskite material La with A-site vacancy x1-CoO3-δPerovskite material La with A site lacking x1-CoO3-δIs densely coated in La0.6Sr0.4Co0.2Fe0.8O3-δA surface. The cathode takes LSCF as a framework, the cathode material is the most extensive material applied to a zirconium-based electrolyte medium temperature (600-850 ℃), and the core-shell structure is actually coated by nano particles and not coated by a nano film, so that the battery performance is ensuredEnergy and life, and also a drawback of requiring the addition of a cerium-based separator between the electrolyte and the cathode of the battery.
The functional layer in the cathode in the prior art is obtained by sintering Sr-containing perovskite (such as LSCF) and oxygen ion conductor material (such as GDC) after mechanical mixing, and the current collecting layer is obtained by sintering Sr-containing perovskite (such as LSCF). The cathode structure prepared by mechanically mixing and sintering the powder has the defects of over coarse microstructure of the cathode material, poor dispersibility, high sintering and forming temperature (higher than 1300 ℃) and the like. In addition, most of the current researches on the cathode coating structure form dispersed nano-particle coating, and cannot form a continuous film coating structure; and the electrolyte is directly prepared on the Sr-containing perovskite cathode framework, the electrolyte and the Sr-containing perovskite porous material are in direct contact, and the problems of higher temperature in the preparation process and Sr segregation caused in the battery operation process still exist, so that an isolating layer needs to be added in the single battery structure when the single battery is prepared.
In summary, although there is a method for modifying the cathode and the electrolyte in the current solid oxide battery structure, the problems of insufficient modification of the cathode, high temperature of the preparation process, serious Sr segregation, etc. still cannot be overcome, so an isolation layer still needs to be added between the electrolyte and the cathode, and the preparation process is complicated, and compactness and battery life cannot be guaranteed.
Therefore, the optimization of the battery structure can be used for preparing the high-performance and long-life batteries in batches by applying a simple and economic process, and is the key for the commercial operation of the solid oxide batteries in China.
Disclosure of Invention
In order to solve the technical problems, the invention provides a zirconium-based anode-supported solid oxide cell without an isolation layer, which can be a Solid Oxide Fuel Cell (SOFC) or a Solid Oxide Electrolytic Cell (SOEC), wherein the cell can effectively control Sr element segregation under the conditions of cell preparation and working by covering a continuous nano-film structure on the surface of a cathode, and can omit GDC (Gd) z Ce z1-O2) The isolation layer improves the service life of the battery.
The invention provides a zirconium-based anode-supported solid oxide battery without an interlayer, which sequentially comprises an anode layer, an electrolyte layer and a membrane-coated cathode layer; wherein the anode layer is made of NiO and zirconium-based electrolyte mixed material, and the electrolyte layer is made of zirconium-based electrolyte material; the membrane-coated cathode layer consists of a membrane-coated functional layer and a membrane-coated current collecting layer, the membrane is a full-nano membrane with the thickness of 5-30nm, the membrane is a Sr-based perovskite material or metal oxide, and the membrane is immersed in a precursor mixed solution of a coating material through the cathode layer and is calcined to form a nano membrane coating structure on the surface of the cathode layer.
The film is selected from Sr-doped LaCoFeO and Sr-doped LaCoO3、SrCoO3、SrFeO3And Sr-doped BaCoO3Sr of A vacancy is doped with La1-xCoFeO3-δSr of A vacancy is doped with La1-xCoO3-δAnd barium oxide, wherein the concentration of the precursor mixed solution is 0.01-0.1M, preferably 0.02-0.05M. The thickness of the film is preferably 10 to 20 nm. Wherein x is more than 0 and less than or equal to 1.
The precursor mixed solution comprises metal nitrate of a coating material, a complexing agent and water; the metal nitrate is at least one selected from lanthanum nitrate, strontium nitrate, cobalt nitrate, ferric nitrate and barium nitrate, the concentration ratio of the nitrate is according to the stoichiometric ratio of the membrane substance, and the total molar concentration of the metals in the nitrate is 0.01-0.1M, preferably 0.02-0.05M.
The zirconium-based electrolyte is rare earth metal-doped ZrO2Is selected from Y2O3Stabilized Zirconia (YSZ) or Sc2O3And CeO2Co-doped ZrO2(ScSZ), the doping amount of the rare earth metal element is 8-10%.
The NiO and the zirconium-based electrolyte materials in the anode layer can be mixed and used in different proportions, and can also be used in a way of being divided into two layers.
In the cathode layer, the functional layer adopts CeO doped with gadolinium oxide2Skeleton Gd z Ce z1-O2 , 0< z <1 (GDC)。
The current collecting layer is Sr-based perovskite material with mixed ion conductorMaterial, in particular selected from SrCoO3、SrFeO3Sr-doped LaCoFeO3 Sr-doped LaCoO3And Sr-doped BaCoO3One or more of them.
The film is selected from perovskite material or metal oxide containing Sr radical, specifically Sr doped LaCoO3(i.e., LSC), SrCoO3、SrFeO3And Sr-doped BaCoO3Sr-doped LaCoFeO3 (i.e., LSCF), A-site vacancy (i.e., perovskite material ABO)3Mesogen defect) of a perovskite material containing an Sr group or barium oxide.
The film is preferably Sr-doped LaCoFeO3Sr-doped LaCoO3Sr of A vacancy is doped with La1-xCoFeO3-δSr of A vacancy is doped with La1-xCoO3-δCan effectively improve the efficiency of the battery.
Wherein, Sr is doped with LaCoFeO3-δGeneral formula is La x Sr x1-Co y Fe y1-O3-δ（LSCF，0<x<1，0<y<1) Sr-doped LaCoO3Of the general formula La x Sr x1-CoO3-δ（LSC，0<x<1) And delta is a value for maintaining the compound electrically neutral, 0<δ<3。
More preferably La0.6Sr0.4Co0.2Fe0.8O3-δ， La0.6Sr0.4CoO3-δ， La0.55Sr0.45Co0.2Fe0.8O3-δ， La0.55Sr0.45CoO3-δ（0<δ<3) One or more of (a).
The perovskite material of the cathode current collector layer may be the same as or different from the membrane material. Generally, LSCF, LSC and their a-vacancy perovskite materials have better ion and electron conduction effects, and are the better choices for intermediate-temperature solid oxide batteries, but because of poor chemical compatibility with electrolytes, cerium-based interlayers are required to be added for preparing the batteries.
The film-coated cathode layer prepared by the invention realizes the continuous nanometer film uniformly coated on the functional layer and the current collecting layer, optimizes the microstructure of the cathode layer, and can prevent the segregation of Sr without a traditional cerium-based isolation layer in the preparation of a single cell structure because the preparation temperature is low (can be lower than 1000 ℃) and the operation temperature is not high (about 750 ℃).
As can be seen from the attached figure 4 in the specification, the nano-film structure prepared in the embodiment 1 of the invention has good continuity, and the uniform full-nano-film structure with the thickness of 10 nm is formed on the surface of the cathode layer by the whole coating film. On one hand, the full-nano film coating structure can enlarge a three-phase interface, improve the oxygen ion transmission efficiency and optimize the performance of the battery; on the other hand, the full-nano film coating structure can lead oxygen ions to be diffused from the surface to the bulk phase and almost all the bulk phase to be transmitted, thereby greatly shortening the electron transmission path, and still maintaining the effect and the service life of the battery even under the condition of no isolation layer. Moreover, the Sr crystal phase in the structure of the nano coating film is more stable, and the Sr segregation problem is not easy to occur.
The thickness of the film is 5 to 30nm, preferably 10 to 20 nm.
If the thickness of the film is large, a dispersion structure of nanoparticles tends to be formed more, and the coating uniformity of nanoparticles cannot be satisfied, affecting the battery performance and life. If the film thickness is insufficient, a continuous film structure cannot be formed, and the coating is insufficient, so that the segregation of Sr cannot be prevented, which affects the battery life.
Solid oxide fuel cell SOFC types include tubular, flat tubular, and planar structures.
In addition, the invention provides a preparation method of the zirconium-based anode-supported solid oxide battery without the isolation layer, which comprises the steps of firstly preparing an anode support body, forming an electrolyte layer on the anode support body to obtain a half battery with a compact electrolyte layer, then forming a cathode layer on the surface of the compact electrolyte of the half battery, preparing a membrane-coated cathode layer structure by adopting a wet impregnation process, and finally obtaining the solid oxide battery without the isolation layer.
The method specifically comprises the following steps:
(1) pretreatment of anode powder: and mixing, drying and sieving the anode powder to obtain the pretreated anode powder.
The anode powder is NiO powder and zirconium-based electrolyte powder; and mixing the anode powder by adopting a ball milling mode, wherein a planetary ball mill can be adopted for ball milling.
The drying temperature is 50-100 ℃, and the drying time is 1-5 h.
The sieving parameter is 100-300 meshes.
(2) Preparing an anode support: and (2) forming the pretreated anode powder obtained in the step (1) into a film blank, namely an anode support.
One of the processes of tape casting, dry pressing or extrusion and the like can be used in the forming process, wherein the anode support body formed by dry pressing and extrusion needs to be pre-sintered, the pre-sintering temperature is 900-. The green body produced by the casting process may not require treatment.
(3) Preparing a half cell with a compact electrolyte layer: and (3) forming a zirconium-based electrolyte layer on the anode support in the step (2), and sintering at high temperature to obtain the half cell with the compact electrolyte layer.
The zirconium-based electrolyte is rare earth metal-doped ZrO2Is selected from Y2O3Stabilized Zirconia (YSZ) or Sc2O3And CeO2Co-doped ZrO2(ScSZ), the doping amount of the rare earth metal element is 8-10%, and YSZ is preferred.
The forming process is that the solution of the electrolyte material is obtained on the anode support body through the processes of tape casting, spraying, dipping, lifting, silk-screen printing and the like.
The dip-coating process is specifically to obtain a dip solution by mixing electrolyte material powder, a solvent and a dispersing agent and performing ultrasonic treatment, and dip, lift and bake the anode support body.
The solvent is preferably isopropanol, the dispersant is preferably castor oil, and the concentration of the electrolyte impregnation liquid is 5% -15%.
The temperature of the high-temperature sintering is 1250-1350 ℃, and the time is 3-8 h, so that the half cell with the compact electrolyte layer is obtained.
(4) Preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: and (4) sequentially forming a functional layer and a current collecting layer on the surface of the compact electrolyte layer of the half-cell obtained in the step (3), sintering, obtaining a cathode layer on the surface of the electrolyte layer, soaking the precursor mixed solution of the coating material into the obtained cathode layer, calcining, and forming a film coating structure on the surface of the cathode layer to obtain the isolation-layer-free zirconium-based anode-supported solid oxide cell with the film-coated cathode layer.
The sintering temperature is 800-1000 ℃, preferably 800-900 ℃, and the time is 2-5 h.
In the cathode layer, the functional layer adopts CeO doped with gadolinium oxide2Skeleton GdzCe1-zO2，0< z <1 (GDC)。
In the cathode layer, the current collecting layer is a perovskite material containing Sr group and provided with mixed ion conductor, and is specifically selected from Sr-doped LaCoO3、SrCoO3、SrFeO3Sr-doped LaCoFeO3And Sr-doped BaCoO3One or more of (a).
The film is selected from perovskite material or metal oxide containing Sr radical, specifically Sr doped LaCoO3(i.e., LSC), SrCoO3、SrFeO3And Sr-doped BaCoO3Sr-doped LaCoFeO3 (i.e., LSCF), A-site vacancy (i.e., perovskite material ABO)3Mesogen defect) of a perovskite material containing an Sr group or barium oxide.
Wherein, Sr is doped with LaCoFeO3General formula is La x Sr x1-Co y Fe y1-O3-δ（LSCF，0<x<1，0<y<1) Sr-doped LaCoO3General formula is La x Sr x1-CoO3-δ（LSC，0<x<1) 。
More preferably La0.6Sr0.4Co0.2Fe0.8O3-δ， La0.6Sr0.4CoO3-δ， La0.55Sr0.45Co0.2Fe0.8O3-δ， La0.55Sr0.45CoO3-δ（0<δ<3) One or more of (a).
The cathode layer can be formed by a spraying or silk-screen process. The method comprises the steps of preparing slurry from material powder of a functional layer and a current collecting layer and spraying solvent or silk-screen glue, and then forming the slurry on a half cell through a spraying or silk-screen process.
The silk-screen printing glue in the silk-screen printing process is prepared by dissolving ethyl cellulose in terpineol to form 6-8wt% of ethyl cellulose terpineol. The solvent commonly used in the spray coating process is absolute ethyl alcohol.
In the dipping process, a trace sample injector is adopted to inject a dipping solution into the sintered cathode layer, wherein the dipping solution is a precursor mixed solution of the coating material and comprises metal nitrate of the coating material, a complexing agent and water; the metal nitrate is at least one selected from lanthanum nitrate, strontium nitrate, cobalt nitrate, ferric nitrate and barium nitrate, the concentration ratio of the nitrate is according to the stoichiometric ratio of the membrane substance, and the total molar concentration of the metals in the nitrate is 0.01-0.1M, preferably 0.02-0.05M.
The complexing agent is urea, and the molar ratio of the urea to the metal ions is 1: 8-30, preferably 1: 10-20.
Calculated based on the volume of the cathode layer material, the impregnation amount is 10-40 mL/cm3(based on a GDC porous skeleton matrix having a porosity of 50%), preferably 20 to 30 mL/cm3。
The calcination temperature is 700-900 ℃; the calcination time is 1-3 h.
The thickness of the coating film is 5-30nm, preferably 10-20 nm.
Most of the existing cathode layer structures are obtained by mechanically mixing perovskite powder and then merging and sintering the perovskite powder by a screen printing process, wherein a functional layer is obtained by mechanically mixing Sr-containing perovskite (such as LSCF) and an oxygen ion conductor material (such as GDC) according to the mass ratio of 1:1 and then sintering the Sr-containing perovskite (such as LSCF). The cathode structure prepared by mechanically mixing and sintering the powder has the defects of over coarse microstructure of the cathode material, poor dispersibility, high sintering and forming temperature (higher than 1300 ℃) and the like. In addition, most of the current researches on the cathode coating structure form dispersed nano-particle coating, and cannot form a continuous film coating structure; and the preparation is directly carried out on the Sr-containing perovskite cathode skeleton, the electrolyte is in direct contact with the Sr-containing porous material, and the problems of higher temperature in the preparation process and Sr segregation caused in the battery operation process still exist, so that an isolating layer still needs to be added when a single battery is prepared.
The invention adopts the screen printing technology to directly and sequentially prepare the porous oxygen ion conductor (such as GDC) and the Sr-containing perovskite cathode layer on the surface of the electrolyte (such as YSZ), the Sr-containing perovskite material in the structure is not directly contacted with the electrolyte, and the sintering preparation temperature is lower, thereby avoiding the segregation of Sr element in the preparation process; and then preparing a film coating structure by adopting wet impregnation, and forming a uniform nano film coating structure (as can be seen from figures 2 and 4) on the micron-sized porous material of the cathode to form a cathode functional layer with a nano structure and a cathode current collecting layer structure with the nano structure. Compared with a porous micron structure containing Sr perovskite in the current-collecting layer, at the operation temperature of the battery (about 750 ℃), the Sr crystalline phase in the nano-film is more stable and is not easy to segregate.
Moreover, as can be seen from the attached figure 8 in the specification, the cathode layer before coating is a micron porous structure (a porous GDC functional layer and a porous LSCF current collector layer), and the surface of the coated (right) cathode layer is provided with a layer of nano film, so that the interface after coating is more stable and uniform, Sr in the cathode structure is more stable, the segregation problem is avoided, and the stability of the battery is improved.
The cathode layer structure design optimizes the microstructure of the cathode, the temperature of the whole cathode layer preparation process is lower than 1000 ℃, Sr segregation cannot be generated, and therefore the service life of the battery is influenced.
In at least one embodiment, a functional layer skeleton (GDC skeleton) and a current collecting Layer (LSFC) are sequentially formed on the surface of an electrolyte (such as YSZ), and a perovskite film (LSCF film) structure is further prepared on the basis of the functional layer skeleton (GDC skeleton) and the current collecting layer (LSCF film), so that the functional layer (GDC film-coated with LSCF) and the current collecting layer (LSCF film-coated with LSCF) are uniformly and continuously coated on a cathode material, the Sr-containing perovskite porous material of the current collecting layer is not directly contacted with the electrolyte, the preparation temperature is low, and the Sr segregation problem is radically solved. Furthermore, the cathode structure coated by the film only transmits through a bulk phase, so that the ion migration path is greatly shortened, the performance of the battery is ensured, and Sr segregation is effectively prevented on the basis of ensuring that the battery has a good electrical effect.
The invention has the advantages that:
1. the invention discloses an SOC structure battery without an isolation layer for the first time, which optimizes the microstructure of a cathode material, constructs a cathode structure coated with a full-nano continuous film, and controls the thickness, uniformity and continuity of the coated film. Through a simple film coating structure, the cathode material of the battery can be prevented from reacting with the electrolyte material, and the stability and the service life of the battery can still be ensured under the condition of no Ce isolating layer.
2. According to the invention, the membrane precursor solution can be uniformly permeated into the functional layer and the current collecting layer through the precursor solution of the membrane material impregnated by the formed cathode layer liquid phase, and sintered at the temperature lower than 1000 ℃, so that a membrane coating structure is formed on the surfaces of the functional layer and the current collecting layer, thereby obtaining the full-nano continuous membrane-coated cathode structure, not only enlarging a three-phase interface, but also realizing oxygen ion phase diffusion, greatly reducing an oxygen ion migration path and improving the battery performance.
3. In the preparation process of the cathode layer, the simple forming process (such as screen printing and spraying) is adopted, the preparation temperature is low, the cathode layer can be obtained without sintering at high temperature, and the Sr-containing perovskite porous framework material is not directly contacted with the electrolyte by adopting a more stable and uniform nano-film coating structure, so that Sr segregation is not generated to generate SrZrO3The preparation of a compact cerium-based isolating layer film is cancelled, the preparation process of the battery is greatly simplified, the preparation cost is reduced, and the battery can still pass through long-term operation conditions (750 ℃, over 800 hours)Can keep good service performance and prolong the service life of the battery.
4. The preparation process of the non-isolation layer SOFC structure battery is simple, the structure of a commercial battery is simplified, the process preparation difficulty is reduced, the preparation process of a compact isolation layer is omitted, industrial mass production is easy to realize, the universality is high, the battery preparation difficulty is reduced, the industrial mass production is suitable, the preparation method is particularly suitable for the preparation of the zirconium-based electrolyte battery, and the preparation method has important significance for the industrial popularization of the SOFC in China.
Drawings
Fig. 1 is a schematic diagram of a cell structure without an isolation layer.
Figure 2 is a schematic of a membrane-encased cathode layer.
Fig. 3 is a cross-sectional profile (SEM) of the cell without separator in example 1.
Fig. 4 is a microscopic Topography (TEM) of the cathode cladding film.
Fig. 5 is a graph of the stability of the battery in the embodiment 1.
Fig. 6 is a stability plot for the comparative example 2 (NiO-YSZ/LSCF with GDC separator) cell.
Fig. 7 is a current commercial universal cell configuration.
Fig. 8 is a micro-topography (SEM) of the example 1 cathode material before (left) and after (right) cladding.
Fig. 9 is a SOFC cell power output diagram.
Wherein 1 is a cathode layer, 2 is a dense electrolyte layer, 3 is an anode layer, 4 is a coating film structure, and 5 is a cathode functional layer (doped CeO)2Skeleton), 6 is a cathode current collector layer (perovskite material), 7 is a cathode layer of the cell having a continuous membrane structure, 8 is a YSZ electrolyte layer of the cell, 9 is a NiO-YSZ anode layer, and 10 is an LSCF clad membrane.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
(1) Pretreatment of anode powder: commercial NiO and 8% Y were selected2O3-ZrO2(YSZ), adding ethanol and zirconia balls according to the mass ratio of 1:1, performing ball milling pretreatment for 24 hours, drying after ball milling, and sieving with a 200-mesh sieve to obtain pretreated anode powder.
(2) Preparing an anode support: and (2) carrying out dry pressing on the pretreated anode powder obtained in the step (1), and presintering at 1000 ℃ to obtain the pre-sintered NiO-YSZ anode support body.
(3) Preparing a half cell with a compact electrolyte layer: mixing YSZ powder, isopropanol and castor oil according to a ratio of 1:10:0.01, performing ultrasonic treatment for 2 hours, and sieving the suspension with a 200-mesh sieve; and (3) soaking the pre-sintered NiO-YSZ anode support body obtained in the step (2) in the solution, slowly pulling out the solution after the solution stays for a moment, drying the solution, and calcining the dried solution at 1350 ℃ for 5 hours to obtain the anode-supported half cell with the compact YSZ film.
(4) Preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: separately mixing commercial Gd0.1Ce0.9O (GDC) powder and La0.6Sr0.4Co0.2Fe0.8O3-δGrinding the (LSCF) powder and the mixture of 6wt% of ethyl cellulose terpineol for 2 hours, and respectively preparing silk-screen slurry for later use. Silk-screen printing is carried out on the anode support half cell obtained in the step (3) by using a screen printer according to the sequence of GDC and LSCF, and sintering is carried out for 2 hours at 900 ℃ to obtain a sintered cathode layer;
according to La0.6Sr0.4Co0.2Fe0.8O3-δPreparing a solution of lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate according to a stoichiometric ratio, simultaneously adding urea as a complexing agent to obtain an impregnation solution, injecting the impregnation solution into the sintered cathode layer by adopting a microsyringe, wherein the metal molar concentration of the impregnation solution is 0.025M, the molar ratio of metal ions to the urea is 1:10, and the dosage of the impregnation solution is 30 mL/cm based on the volume of the cathode layer3And then calcining at 800 ℃ for 2h to finally coat the cathode layer with a film (LSCF), wherein the thickness of the coating film is about 10 nm, thereby obtaining the zirconium-based anode-supported solid oxide battery without the isolating layer.
Example 2
(1) Pretreatment of anode powder: commercial NiO and 8% Y were selected2O3-ZrO2(YSZ), adding ethanol and zirconia balls according to the mass ratio of 1:1, performing ball milling pretreatment for 24 hours, drying after ball milling, and sieving with a 200-mesh sieve to obtain pretreated anode powder.
(2) Preparing an anode support: and (2) carrying out dry pressing on the pretreated anode powder obtained in the step (1), and presintering at 1000 ℃ to obtain a presintering NiO-YSZ anode support body.
(3) Preparing a half cell with a compact electrolyte layer: mixing YSZ powder, isopropanol and castor oil according to a mass ratio of 1:10:0.01, performing ultrasonic treatment for 2 hours, and sieving a suspension with a 200-mesh sieve; and (3) soaking the pre-sintered NiO-YSZ anode support body obtained in the step (2) in the solution, slowly pulling out the solution after the solution stays for a moment, drying the solution, and calcining the dried solution at 1350 ℃ for 5 hours to obtain the anode-supported half cell with the compact YSZ film.
(4) Preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: separately mixing commercial Gd0.1Ce0.9O (GDC) powder and La0.6Sr0.4Co0.2Fe0.8O3-δGrinding the (LSCF) powder and 6 wt.% of ethyl cellulose terpineol mixture for 2 hours to prepare the silk-screen printing slurry. Silk-screen printing is carried out on the anode supporting half cell obtained in the step (3) by using a screen printer according to the sequence of GDC and LSCF, and sintering is carried out for 2 hours at 900 ℃ to obtain a sintered cathode layer;
according to La0.6Sr0.4CoO3-δPreparing a mixed solution of 0.025M lanthanum nitrate, strontium nitrate and cobalt nitrate according to a stoichiometric ratio, simultaneously adding urea as a complexing agent to obtain an impregnation solution, injecting the impregnation solution into the sintered cathode layer by using a microsyringe, wherein the molar concentration of metal ions in the impregnation solution is 0.025M, the molar ratio of the metal ions to the urea in the impregnation solution is 1:10, and the dosage of the impregnation solution (based on the volume of the cathode layer) is 30 mL/cm3And then calcining at 800 ℃ for 2h, and finally coating the cathode layer with a film (LSC) with the thickness of about 10 nm to obtain the barrier-layer-free zirconium-based anode-supported solid oxide battery.
Example 3
(1) Pretreatment of anode powder: commercial NiO and 8% Y were selected2O3-ZrO2(YSZ), adding ethanol and zirconia balls according to the mass ratio of 1:1, performing ball milling pretreatment for 24 hours, drying after ball milling, and sieving with a 200-mesh sieve to obtain pretreated anode powder.
(2) Preparing an anode support: and (2) carrying out dry pressing on the pretreated anode powder obtained in the step (1), and presintering at 1000 ℃ to obtain a presintering NiO-YSZ anode support body.
(3) Preparing a half cell with a compact electrolyte layer: mixing YSZ powder, isopropanol and castor oil according to a ratio of 1:10:0.01, performing ultrasonic treatment for 2 hours, and sieving the suspension with a 200-mesh sieve; and (3) soaking the pre-sintered NiO-YSZ anode support body obtained in the step (2) in the solution, slowly pulling out the solution after the solution stays for a moment, drying the solution, and calcining the dried solution at 1350 ℃ for 5 hours to obtain the anode-supported half cell with the compact YSZ film.
(4) Preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: separately mixing commercial Gd0.1Ce0.9O (GDC) powder and La0.6Sr0.4Co0.2Fe0.8O3-δGrinding the (LSCF) powder and a terpineol mixture of 6wt% of ethyl cellulose for 2 hours to prepare silk-screen printing slurry; and (4) silk-screening the anode support half cell obtained in the step (3) by using a screen printer according to the sequence of GDC and LSCF, and sintering at 900 ℃ for 2h to obtain a sintered cathode layer.
According to La0.55Sr0.45Co0.2Fe0.8O3-δPreparing mixed solution of lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate according to stoichiometric ratio, simultaneously adding urea as complexing agent to obtain impregnation solution, injecting the impregnation solution into the sintered cathode layer by adopting a microsyringe, wherein the molar concentration of metal ions in the impregnation solution is 0.025M, the molar ratio of the metal ions to the urea is 1:10, and the dosage of the impregnation solution (based on the volume of the cathode layer) is 30 mL/cm3And then calcining at 800 ℃ for 2h to ensure that the cathode layer is coated by a film (A vacancy LSCF), and the thickness of the coating film is about 10 nm, thereby obtaining the zirconium-based anode-supported solid oxide battery without the separation layer.
Example 4
(1) Pretreatment of anode powder: commercial NiO and 8% Y were selected2O3-ZrO2(YSZ), adding ethanol and zirconia balls according to the mass ratio of 1:1, performing ball milling pretreatment for 24 hours, drying after ball milling, and sieving with a 200-mesh sieve to obtain pretreated anode powder.
(2) Preparing an anode support: and (2) carrying out dry pressing on the pretreated anode powder obtained in the step (1), and presintering at 1000 ℃ to obtain a presintering NiO-YSZ anode support body.
(3) Preparing a half cell with a compact electrolyte layer: mixing YSZ powder, isopropanol and castor oil according to a ratio of 1:10:0.01, performing ultrasonic treatment for 2 hours, and sieving the suspension with a 200-mesh sieve; and (3) soaking the pre-sintered NiO-YSZ anode support body obtained in the step (2) in the solution, slowly pulling out the solution after the solution stays for a moment, drying the solution, and calcining the dried solution at 1350 ℃ for 5 hours to obtain the anode-supported half cell with the compact YSZ film.
(4) Preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: separately mixing commercial Gd0.1Ce0.9O (GDC) powder and La0.6Sr0.4Co0.2Fe0.8O3-δGrinding the mixture of (LSCF) powder and 6% ethyl cellulose terpineol for 2h to respectively prepare silk-screen printing slurry; and (4) silk-screening the anode support half cell obtained in the step (3) by using a screen printer according to the sequence of GDC and LSCF, and sintering at 900 ℃ for 2h to obtain a sintered cathode layer.
According to La0.6Sr0.4Co0.2Fe0.8O3-δPreparing a mixed solution of lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate according to a stoichiometric ratio, simultaneously adding urea as a complexing agent to obtain an impregnation solution, injecting the impregnation solution into the sintered cathode layer by adopting a microsyringe, wherein the molar concentration of metal ions in the solution is 0.05M, the molar ratio of the metal ions to the urea is 1:20, and the dosage of the impregnation solution (based on the volume of the cathode film) is 30 mL/cm3And then calcining at 800 ℃ for 2h to ensure that the cathode layer is coated by a film (LSCF), and the thickness of the coating film is about 18 nm, thereby obtaining the barrier-layer-free zirconium-based anode-supported solid oxide battery.
Example 5
(1) Pretreatment of anode powder: commercial NiO and 8% Y were selected2O3-ZrO2(YSZ), adding ethanol and zirconia balls according to the mass ratio of 1:1, performing ball milling pretreatment for 24 hours, drying after ball milling, and sieving with a 200-mesh sieve to obtain pretreated anode powder.
(2) Preparing an anode support: and (2) carrying out dry pressing on the pretreated anode powder obtained in the step (1), and presintering at 1000 ℃ to obtain a presintering NiO-YSZ anode support body.
(3) Preparing a half cell with a compact electrolyte layer: mixing YSZ powder, isopropanol and castor oil according to a ratio of 1:10:0.01, performing ultrasonic treatment for 2 hours, and sieving the suspension with a 200-mesh sieve; and (3) soaking the pre-sintered NiO-YSZ anode support body obtained in the step (2) in the solution, slowly pulling out the solution after the solution stays for a moment, and calcining the solution at 1350 ℃ for 5 hours after air drying to obtain the anode support half cell with the compact YSZ film.
(4) Preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: separately mixing commercial Gd0.1Ce0.9O (GDC) powder and La0.6Sr0.4Co0.2Fe0.8O3-δGrinding the (LSCF) powder and a mixture of 6 wt.% ethyl cellulose terpineol for 2 hours to respectively prepare silk-screen printing slurry; and (4) silk-screening the anode support half cell obtained in the step (3) by using a screen printer according to the sequence of GDC and LSCF, and sintering at 900 ℃ for 2h to obtain a sintered cathode layer.
According to La0.6Sr0.4Co0.2Fe0.8O3-δPreparing mixed solution of lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate according to stoichiometric ratio, simultaneously adding urea as complexing agent to obtain impregnation solution, injecting the impregnation solution into the sintered cathode layer by adopting a microsyringe, wherein the molar concentration of metal ions in the solution is 0.09M, the molar ratio of the metal ions to the urea is 1:30, and the dosage of the impregnation solution (based on the volume of the cathode layer) is 30 mL/cm3Then calcining the obtained product at 800 ℃ for 2h to ensure that the cathode layer is coated by a film (LSCF), and the thickness of the coating film is about 30nm, thereby obtaining the zirconium-based anode-supported solid oxide battery without the isolating layer。
Example 6
(1) Pretreatment of anode powder: commercial NiO and 8% Y were selected2O3-ZrO2(YSZ), adding ethanol and zirconia balls according to the mass ratio of 1:1, performing ball milling pretreatment for 24 hours, drying after ball milling, and sieving with a 200-mesh sieve to obtain pretreated anode powder.
(2) Preparing an anode support: and (2) carrying out dry pressing on the pretreated anode powder obtained in the step (1), and presintering at 1000 ℃ to obtain a presintering NiO-YSZ anode support body.
(3) Preparing a half cell with a compact electrolyte layer: mixing YSZ powder, isopropanol and castor oil according to a ratio of 1:10:0.01, performing ultrasonic treatment for 2 hours, and sieving the suspension with a 200-mesh sieve; and (3) soaking the pre-sintered NiO-YSZ anode support body obtained in the step (2) in the solution, slowly pulling out the solution after the solution stays for a moment, drying the solution, and calcining the dried solution at 1350 ℃ for 5 hours to obtain the anode-supported half cell with the compact YSZ film.
(4) Preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: separately mixing commercial Gd0.1Ce0.9O (GDC) powder and La0.6Sr0.4Co0.2Fe0.8O3-δGrinding the (LSCF) powder and the 6% ethyl cellulose terpineol mixture for 2 hours, and respectively preparing silk-screen printing slurry for later use. Silk-screen printing is carried out on the anode supporting half cell obtained in the step (3) by using a screen printer according to the sequence of GDC and LSCF, and sintering is carried out for 2 hours at 900 ℃ to obtain a sintered cathode layer;
according to La0.6Sr0.4Co0.2Fe0.8O3-δPreparing mixed solution of lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate according to a stoichiometric ratio, simultaneously adding urea as a complexing agent, impregnating the mixed solution into the sintered cathode layer, wherein the molar concentration of metal ions in the solution is 0.01M, the molar ratio of the metal ions to the urea is 1:8, and the dosage of the impregnating solution (based on the volume of the cathode layer) is 30 mL/cm3And then calcining at 800 ℃ for 2h to ensure that the cathode layer is coated by a film (LSCF), and the thickness of the coating film is about 6 nm, thereby obtaining the barrier-layer-free zirconium-based anode-supported solid oxide battery.
Example 7
(1) Pretreatment of anode powder: commercial NiO and 8% Y were selected2O3-ZrO2(YSZ), adding ethanol and zirconia balls according to the mass ratio of 1:1, performing ball milling pretreatment for 24 hours, drying after ball milling, and sieving with a 250-mesh sieve to obtain pretreated anode powder.
(2) Preparing an anode support: and (2) carrying out dry pressing on the pretreated anode powder obtained in the step (1), and presintering at 1000 ℃ to obtain a presintering NiO-YSZ anode support body.
(3) Preparing a half cell with a compact electrolyte layer: mixing YSZ powder, isopropanol and castor oil according to a ratio of 1:10:0.01, performing ultrasonic treatment for 2 hours, and sieving the suspension with a 200-mesh sieve; and (3) soaking the pre-sintered NiO-YSZ anode support body obtained in the step (2) in the solution, staying for a moment, slowly pulling out the solution, airing, and calcining at 1300 ℃ for 5 hours to obtain the anode support half cell with the compact YSZ film.
(4) Preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: separately mixing commercial Gd0.1Ce0.9O (GDC) powder and La0.6Sr0.4Co0.2Fe0.8O3-δGrinding the mixture of (LSCF) powder and 8% ethyl cellulose terpineol for 2h, and respectively preparing silk-screen printing slurry for later use; and (4) silk-screening the anode support half cell obtained in the step (3) by using a screen printer according to the sequence of GDC and LSCF, and sintering at 850 ℃ for 2h to obtain a sintered cathode layer.
According to La0.6Sr0.4Co0.2Fe0.8O3-δPreparing a mixed solution of lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate according to a stoichiometric ratio, simultaneously adding urea as a complexing agent to obtain an impregnation solution, injecting the impregnation solution into the sintered cathode layer solution by using a microsyringe, wherein the molar concentration of metal ions is 0.035M, the molar ratio of the metal ions to the urea is 1:16, and the dosage of the impregnation solution (based on the volume of the cathode layer) is 25mL/cm3And then calcining at 800 ℃ for 3h to ensure that the cathode layer is coated by a film (LSCF), and the thickness of the coating film is about 15 nm, thereby obtaining the barrier-layer-free zirconium-based anode-supported solid oxide battery.
Example 8
Steps 1 to 3 are the same as in example 1.
(4) Preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: separately mixing commercial Gd0.1Ce0.9O (GDC) powder and La0.6Sr0.4Co0.2Fe0.8O3-δGrinding the (LSCF) powder and the mixture of 6wt% of ethyl cellulose terpineol for 2 hours, and respectively preparing silk-screen slurry for later use. Silk-screen printing is carried out on the anode supporting half cell obtained in the step (3) by using a screen printer according to the sequence of GDC and LSCF, and sintering is carried out for 2 hours at 900 ℃ to obtain a sintered cathode layer;
preparing barium nitrate solution, adding urea serving as a complexing agent to obtain an impregnation solution, injecting the impregnation solution into the sintered cathode layer by using a microsyringe, wherein the metal molar concentration of the impregnation solution is 0.025M, the molar ratio of metal ions to the urea is 1:9, and the dosage of the impregnation solution is 30 mL/cm based on the volume of the cathode layer3And then calcining at 800 ℃ for 2h to ensure that the cathode layer is coated by a film (barium oxide) with the thickness of about 12 nm, thereby obtaining the zirconium-based anode-supported solid oxide battery without the isolating layer.
Comparative example 1
(1) Pretreatment of anode powder: commercial NiO and 8% Y were selected2O3-ZrO2(YSZ), adding ethanol and zirconia balls according to the mass ratio of 1:1, performing ball milling pretreatment for 24 hours, drying after ball milling, and sieving with a 200-mesh sieve to obtain pretreated anode powder.
(2) Preparing an anode support: and (2) carrying out dry pressing on the pretreated anode powder obtained in the step (1), and presintering at 1000 ℃ to obtain a presintering NiO-YSZ anode support body.
(3) Preparing an electrolyte layer: mixing YSZ powder, isopropanol and castor oil according to a ratio of 1:10:0.01, performing ultrasonic treatment for 2 hours, and sieving the suspension with a 200-mesh sieve; and (3) soaking the pre-sintered NiO-YSZ anode support body obtained in the step (2) in the solution, slowly pulling out the solution after the solution stays for a moment, and calcining the solution at 1350 ℃ for 5 hours after air drying to obtain the anode support half cell with the compact YSZ film.
(4) Preparing a solid oxide battery: respectively give a quotientGd is used as a material for0.1Ce0.9O (GDC) powder and La0.6Sr0.4Co0.2Fe0.8O3-δGrinding the (LSCF) powder and the 6% ethyl cellulose terpineol mixture for 2 hours to prepare the silk-screen printing slurry. And (4) silk-screening the half cell obtained in the step (3) by using a screen printer according to the sequence of GDC and LSCF, and sintering at 900 ℃ for 2h to obtain a sintered cathode layer, thus obtaining the solid oxide cell.
Comparative example 2
Referring to a common commercial battery, a single cell having a separator is prepared, and the battery structure is as shown in fig. 7, and the specific steps include:
(1) pretreatment of anode powder: commercial NiO and 8% Y were selected2O3-ZrO2(YSZ), adding ethanol and zirconia balls according to the mass ratio of 1:1, performing ball milling pretreatment for 24 hours, drying after ball milling, and sieving with a 200-mesh sieve to obtain pretreated anode powder.
(2) Preparing an anode support: and (2) carrying out dry pressing on the pretreated anode powder obtained in the step (1), and presintering at 1000 ℃ to obtain a presintering NiO-YSZ anode support body.
(3) Preparing an electrolyte layer: mixing YSZ powder, isopropanol and castor oil according to a ratio of 1:10:0.01, performing ultrasonic treatment for 2 hours, and sieving the suspension with a 200-mesh sieve; and (3) soaking the pre-sintered NiO-YSZ anode support body obtained in the step (2) in the solution, slowly pulling out the solution after the solution stays for a moment, and calcining the solution at 1350 ℃ for 5 hours after air drying to obtain the anode support half cell with the compact YSZ film.
(4) Preparing an isolation layer: and ball-milling the GDC powder for 24h, drying, sieving with a 200-mesh sieve, and mixing with silk-screen printing glue (6% ethyl cellulose terpineol solution) in a mass ratio of 1:1, and grinding for 2h to obtain GDC silk-screen printing slurry. And (3) screen-printing the GDC isolation layer by using a screen printer, and sintering at 1300 ℃ for 5h after drying to obtain the GDC isolation layer.
(5) Preparing a cathode: will trade La0.6Sr0.4Co0.2Fe0.8O3-δMixing and ball-milling (LSCF) powder and GDC powder according to the mass ratio of 1:1, drying, sieving with a 200-mesh sieve, grinding the mixed powder and a 6% ethyl cellulose terpineol mixture according to the mass ratio of 1:1 for 2 hours to prepare silk-screen printing slurry. And (3) silk-screen printing the mixed LSCF and GDC slurry on a half cell containing a GDC isolation layer by using a screen printer according to the sequence of the functional layer (LSCF + GDC) and the current collecting Layer (LSCF), drying at 100 ℃, continuously silk-screen printing the LSCF slurry on the layer, drying, and sintering at 1200 ℃ for 2h to obtain a cathode layer, thereby obtaining the zirconium-based anode supported solid oxide cell with the isolation layer.
And (3) testing the battery performance:
the cells prepared in the examples and comparative examples were sealed to an alumina test fixture using a laboratory developed seal and the cell performance was tested in a temperature controlled muffle furnace. Heating to 200 ℃ at a speed of 2 ℃/min, preserving heat for 1h, discharging the glue, sealing, heating to 800 ℃ for testing, and cooling to 750 ℃ for constant current discharge after the testing is finished. 3% H is introduced into the anode (hydrogen electrode) side in the SOFC mode test process2H of O2The gas flow rate was controlled at 50sccm, and the cathode (oxygen electrode) side was exposed to the atmosphere, which was an air atmosphere. During the SOEC mode test, the hydrogen electrode (anode in SOFC mode) was tested with 10% H245% steam and 45% CO2The mixed gas of (1) was tested under a 1.5V charging condition in which the total gas flow rate was 50sccm and the oxygen electrode (cathode in SOFC mode) side was exposed to the atmosphere. The test results are shown in table 1. The battery power output testing device adopts a Switzerland Wantong electrochemical workstation (Metrohm Autolab PGSTAT 302), the electrolytic performance and the battery constant current discharge test adopt an American Arbin electrochemical workstation (Arbin), and the test results are shown in Table 1.
Moreover, as can be seen from fig. 1-4 in the specification, under the scanning electron microscope and the transmission electron microscope, the morphological structure of the LSCF nano-film is formed on the functional layer GDC and the current collecting layer LSCF. The flow-collecting layer LSCF is prepared by preparing slurry from LSCF powder silk-screen glue and sintering the slurry to obtain a micron-sized porous grain stacking structure; the coated LSCF film is obtained by in-situ impregnation of a precursor solution, and the form of a continuous nano film and the optimal film thickness are obtained on the basis of a proper impregnation process.
In the battery structure without the isolation layer prepared in embodiment 1 of the present invention, the membrane is continuously coated on the functional layer (GDC skeleton) and the current collecting Layer (LSCF) of the cathode, and the membrane structure is continuous and uniform and has a thickness of about 10 nm.
As can be seen from Table 1 and FIG. 5, the power output of the test of example 1 in the SOFC mode reaches 1.1W/cm at 800 deg.C2At 750 ℃ and at 0.3A/cm2Constant current discharge, the power output decays by 2 percent (namely the power of the battery is reduced by 2 percent) after the battery runs for 400 hours. Under the charging condition of 1.5V at 800 ℃ and in an SOEC mode, the current density is 1.9A/cm2. In comparison, as can be seen from fig. 6, the power output decay has exceeded 6% for the comparative example 2 cell operating around 250 hours.
Figure 33520DEST_PATH_IMAGE001
As can be seen from the example 1 and the comparative examples 1 and 2, the battery with the membrane-coated cathode structure of the invention not only saves the preparation process of the cerium-based interlayer, but also does not need higher temperature in the whole battery preparation process, and the preparation process of the cathode material is lower than 1000 ℃. Moreover, the power output of the single cell reaches 1.1W/cm under the test of 800 ℃ in the SOFC mode2The battery is at 750 ℃ and 0.3A/cm2Run under conditions 840h with less than 5% decay. Under the SOEC mode, 1.5V is applied to voltage for electrolysis at 800 ℃, and the current density reaches 1.9A/cm2。
As can be seen from the example 2 and the comparative examples 1 and 2, the battery with the membrane-coated cathode structure of the invention not only saves the preparation process of the cerium-based interlayer, does not need higher temperature in the whole battery preparation process, and the preparation process of the cathode material is lower than 1000 ℃, but also the power output of the single battery can reach 1.6W/cm under the SOFC mode at 800℃ test2The battery is at 750 ℃ and 0.5A/cm2Run under conditions 840h with less than 1% decay. Under the SOEC mode, 1.5V is applied to voltage for electrolysis at 800 ℃, and the current density reaches 2.6A/cm2. The SOC solid oxide battery can realize high-efficiency conversion between chemical energy and electric energy.
The single cell without the addition of the cerium-based interlayer (comparative example 1) not only has reduced cell effect but also has poor cell stability, and the cell power is 9.4 percent already in the SOFC mode when the cell is operated for 230hAnd after 400 hours of operation, the battery power attenuation rate is 18.2 percent higher. Under the SOEC mode, 1.5V is applied to voltage for electrolysis at 800 ℃, and the current density is only 1.3A/cm2。
Although the efficiency of the ordinary commercial single cell (comparative example 2) added with the cerium-based interlayer can be ensured, the stability can not meet the requirement, the power of the single cell in the SOFC mode is attenuated by 7.2% after the single cell operates for 230 hours, the power attenuation rate of the single cell is 13.7% after the single cell operates for 400 hours, the service life of the single cell is short, and the interlayer preparation process is complex. Electrolyzing at 800 deg.C under 1.5V in SOEC mode with current density of 1.6A/cm2。
As can be seen from examples 1 to 3 and 8, the film material is preferably LSCF, LSC, a-deficient LSCF, or a-deficient LSC, and the film-coated cathode structure (the continuous uniform film coats the functional layer and the current collecting layer) of the present invention is formed, so that the battery efficiency can be maintained, the battery stability can be further enhanced, and the battery service life can be prolonged.
As is apparent from fig. 9 in the specification, examples 1 and 2 of the present invention have good SOFC output power compared to the SOFC cell prepared in comparative example 1.
From the examples 1, 4-7, it can be seen that the coating effect is better when the film thickness is 5-30nm, the cell efficiency is better than that of a common commercial SOFC single cell, and the cell stability is greatly improved; especially in the range of 10-20 nm, after 840 hours of operation, the power attenuation of the battery is still lower than 5%, the design of an interlayer is omitted, the preparation process of a single battery is greatly simplified, and the method is suitable for industrial production.

Claims (10)

1. A zirconium-based anode-supported solid oxide cell without an isolation layer is characterized by sequentially comprising an anode layer, an electrolyte layer and a membrane-coated cathode layer; wherein the anode layer is made of NiO and zirconium-based electrolyte mixed material, and the electrolyte layer is made of zirconium-based electrolyte material; the membrane-coated cathode layer consists of a membrane-coated functional layer and a membrane-coated current collecting layer, wherein the membrane is a full-nano membrane with the thickness of 5-30nm, the membrane is a Sr-based perovskite material or metal oxide, and a nano membrane-coated structure is formed on the surface of the cathode layer by impregnating the cathode layer with a precursor mixed solution of a coating material and calcining the impregnated cathode layer.
2. The solid oxide cell of claim 1, wherein the film is selected from Sr doped laccofeo3(ii) a Sr-doped LaCoO3、SrCoO3、SrFeO3(ii) a Sr-doped BaCoO3(ii) a Sr doped La of A vacancy1-xCoFeO3-δ(ii) a Sr doped La of A vacancy1-xCoO3-δStarting the process; one or more of barium oxide.
3. The solid oxide cell of claim 2, wherein the precursor mixed solution comprises a metal nitrate of a coating material, a complexing agent, and water; the metal nitrate is at least one of lanthanum nitrate, strontium nitrate, cobalt nitrate, ferric nitrate and barium nitrate, the concentration proportion of the nitrate is according to the stoichiometric ratio of the film substance, and the total molar concentration of the metal in the nitrate is 0.01-0.1M.
4. The solid oxide cell of claim 1, wherein the membrane has a thickness of 10-20 nm.
5. The solid oxide cell of claim 1, wherein the zirconium-based electrolyte is a rare earth doped ZrO2Is selected from Y2O3Stabilized Zirconia (YSZ) or Sc2O3And CeO2Co-doped ZrO2（ScSZ）；
The functional layer is CeO doped with gadolinium oxide2Skeleton Gd z Ce z1-O2 , 0< z <1；
The current collecting layer is a Sr-based perovskite material, and is specifically selected from SrCoO3、SrFeO3Sr-doped LaCoO3Sr-doped LaCoFeO3And Sr-doped BaCoO3One or more of (a).
6. A method for the preparation of a barrier-free zirconium based anode-supported solid oxide cell according to any one of claims 1 to 5, comprising the steps of: preparing an anode support body, forming an electrolyte layer on the anode support body to obtain a half cell with a compact electrolyte layer, then forming a cathode layer on the compact electrolyte surface of the half cell, and preparing a membrane-coated cathode layer structure by adopting a wet impregnation process to finally obtain the zirconium-based anode-supported solid oxide cell without the isolation layer.
7. The method of claim 6, comprising the steps of:
(1) pretreatment of anode powder: mixing, drying and sieving the anode powder to obtain pretreated anode powder;
(2) preparing an anode support: molding the pretreated anode powder obtained in the step (1) into a film blank, namely an anode support body;
(3) preparing a half cell with a compact electrolyte layer: forming an electrolyte layer on the anode support body in the step (2), and sintering at high temperature to obtain a half cell with a compact electrolyte layer;
(4) preparation of barrier-free zirconium-based anode-supported solid oxide cells with membrane-coated cathode layer: and (4) sequentially forming a functional layer and a current collecting layer on the surface of the compact electrolyte layer of the half-cell obtained in the step (3), sintering, obtaining a cathode layer on the surface of the electrolyte layer, soaking the cathode layer in a precursor mixed solution of the coating material, calcining, and forming a film coating structure on the surface of the cathode layer to obtain the isolation layer-free zirconium-based anode-supported solid oxide cell with the film-coated cathode layer.
8. The preparation method according to claim 7, wherein the precursor mixed solution in the step (4) includes a metal nitrate of the coating material, a complexing agent and water; the metal nitrate is selected from at least one of lanthanum nitrate, strontium nitrate, cobalt nitrate, ferric nitrate and barium nitrate, and the concentration proportion of the nitrate is in accordance with the stoichiometric ratio of the film substance;
the complexing agent is urea, and the molar ratio of the urea to the metal ions is 1: 10-30 parts of;
calculated based on the volume of the cathode layer material, the impregnation amount is 10-40 mL/cm3。
9. The method as claimed in claim 7, wherein the sintering temperature in step (4) is 800-1000 ℃ and the time is 2-5 h; the calcination temperature is 700-900 ℃; the calcination time is 1-3 h.
10. The preparation method according to claim 7, wherein the anode powder in step (1) is NiO powder and zirconium-based electrolyte powder, and the anode powder is mixed by ball milling, and the sieving parameter is 100-300 mesh; the forming process in the step (3) is that the solution of the electrolyte material is obtained on the anode support body through casting, spraying, dip-coating or silk-screen technology; the temperature of the high-temperature sintering is 1250-;
the dipping and pulling process is to mix electrolyte material powder, solvent and dispersant and carry out ultrasonic treatment to obtain dipping solution, and then the anode support body is dipped, pulled and roasted to obtain the electrolyte material powder; the solvent is isopropanol, and the dispersant is castor oil; the concentration of the electrolyte impregnation liquid is 5% -15%;
the spraying or silk-screen process is to prepare slurry from the electrolyte material powder and a spraying solvent or silk-screen glue, and then spray or silk-screen the slurry.
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