CN113871674B - CGO electrolyte-based MS-SOEC structure and preparation method thereof - Google Patents

CGO electrolyte-based MS-SOEC structure and preparation method thereof Download PDF

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CN113871674B
CN113871674B CN202111195573.0A CN202111195573A CN113871674B CN 113871674 B CN113871674 B CN 113871674B CN 202111195573 A CN202111195573 A CN 202111195573A CN 113871674 B CN113871674 B CN 113871674B
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electrolyte
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cgo
soec
powder
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CN113871674A (en
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张梦茹
王恩华
刘亚迪
胡浩然
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Beijing Siweite New Energy Technology Co ltd
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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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • 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
    • 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
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention provides a CGO electrolyte-based MS-SOEC structure and a preparation method thereof, relating to the technical field of fuel cells. The CGO electrolyte-based MS-SOEC structure comprises a metal substrate, a cathode layer, an electrolyte layer and an anode layer, wherein the cathode layer is deposited on the upper surface of the metal substrate, the electrolyte layer is deposited on the cathode layer, the electrolyte layer is overlapped with the cathode layer, and the anode layer is deposited on the electrolyte layer. The metal support type solid oxide fuel electrolytic cell adopting the CGO electrolyte can realize the purpose that the solid oxide fuel electrolytic cell operates at a medium-low temperature, thereby reducing the operation cost of the SOEC and realizing the industrial development of the SOEC. 2) At different operating temperatures, the input voltage of the CGO electrolyte based MS-SOEC is equal to the input voltage of the three layer electrolyte based MS-SOEC when a certain current density is reached.

Description

CGO electrolyte-based MS-SOEC structure and preparation method thereof
Technical Field
The invention relates to the technical field of fuel cells, in particular to a CGO electrolyte-based MS-SOEC structure and a preparation method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) or SOEC is a device having a completely Solid structure that operates in a high temperature environment, and is a very promising technology, and has the advantages of high energy conversion efficiency, environmental friendliness, fuel diversity, and the like. The key to realizing the SOEC industrialization is to reduce the cost of the electrolytic cell, and an effective method for reducing the cost is to reduce the operating temperature of the electrolytic cell. The selection of the electrolyte of the SOEC is very critical, on one hand, the electrochemical properties of the material determine the performance of the electrolytic cell, and on the other hand, the microstructure and atomic arrangement of the interface between the electrolyte and the electrode strongly influence the electrochemical properties of the interface, and further influence the performance of the electrolytic cell. Since the related research on SOEC is less, and it is the reversible reaction of SOFC, the related research work is carried out with reference to the related research on SOFC. GB2368450B describes a metal supported CGO electrolyte based solid oxide fuel cellThe cell can be operated at relatively low temperature and with low polarization losses. Ceria is more easily sintered to compact, has higher ionic conductivity, and can be operated at lower temperatures than electrolytes such as zirconia, which can be run to 500 ℃ in practical fuel cells if the electrolyte is in the form of a thick film (typically 10-15um thick). In addition, the CGO electrolyte method adopting metal support has outstanding advantages, and the cost is lower by adopting ferrite stainless steel firstly; second, the use of a metal substrate facilitates the elimination of ceramic to metal seal sealing problems using conventional metal joining techniques, such as welding and the like. Unlike zirconia, ceria is not chemically stable and can be reduced when exposed to a reducing atmosphere at high temperatures, where Ce 4+ The ions can be partially reduced to Ce 3+ Ions. This reduction causes the CGO to exhibit some mixed ionic/electronic conductivity, resulting in internal shorting of the cell, resulting in a loss of open circuit voltage and a corresponding loss of cell efficiency. US10897056B2 proposes a three-layer electrolyte MS-SOFC (Metal Support-Solid Oxide Fuel Cell, MS-SOFC for short) structure for the leakage electron phenomenon of CGO electrolyte base at high temperature, and a very thin stable YSZ layer and a thinner CGO layer are deposited on top of a thicker CGO electrolyte layer. A stable YSZ film is deposited in the electrolyte to prevent internal cell shorting due to the mixed ion/electron conductivity of the CGO electrolyte; since the YSZ layer is very thin, its resistance to oxygen ion transport is low enough that low temperature operation can still be performed. On the other hand, the thinner CGO layer above the YSZ layer film serves to prevent interfacial reaction between the electrolyte and the anode. Compared with the prior Ceres CGO electrolyte-based MS-SOFC, after a YSZ layer and a CGO film are further deposited on the CGO electrolyte, the phenomenon that electrons leak from the MS-SOFC in the operation process can be effectively avoided, and the output performance of the MS-SOFC is effectively improved. However, the structure of the three-layer electrolyte has higher requirements on the material preparation and design process of the battery, and the investment cost is increased. Research by Ceres corporation has shown that, at typical operating current densities, current leakage within the battery is nearly negligible and can occur at temperatures of 600 ℃ or lessAnd managing in the case of an open circuit.
Therefore, the invention aims to find the optimal operating condition range of the MS-SOEC (Metal Support-Solid Oxide Electrolysis Cell, MS-SOEC for short) based on the CGO electrolyte, thereby achieving the optimal output performance on the basis of lower operating cost.
Disclosure of Invention
The invention aims to provide a CGO electrolyte-based MS-SOEC structure and a preparation method thereof, which adopt a pure mechanical structure, have low cost and low power consumption, improve the reliability of the conventional PEMFC engine, reduce the total code amount and reduce the failure rate of the engine.
In order to realize the purpose, the following technical scheme is provided:
the invention provides a CGO electrolyte-based MS-SOEC structure which comprises a metal substrate, a cathode layer, an electrolyte layer and an anode layer, wherein the cathode layer is deposited on the upper surface of the metal substrate, the electrolyte layer is deposited on the cathode layer, the electrolyte layer is overlapped with the cathode layer, and the anode layer is deposited on the electrolyte layer.
Further, a plurality of drill holes are drilled in the central area of the metal substrate.
Further, the diameter of the drill hole is 10-30um.
Further, the CGO electrolyte-based MS-SOEC structure includes at least one of the following:
the first method is as follows: the thickness of the metal substrate is 200-300um;
the second method comprises the following steps: the thickness of the cathode layer is 15 +/-0.5 um;
the third method comprises the following steps: the thickness of the electrolyte layer is 10-15um;
the method is as follows: the thickness of the anode layer is 25 + -0.5 um.
Further, the CGO electrolyte-based MS-SOEC structure includes at least one of the following:
the first method is as follows: the metal substrate is a foil plate;
the second method comprises the following steps: the cathode layer is made of porous nickel-CGO composite ceramic.
Further, the CGO electrolyte-based MS-SOEC is: the total thickness of the CGO electrolyte is 15.1 um.
The invention also provides a preparation method of the CGO electrolyte matrix MS-SOEC structure, wherein the preparation method of the electrolyte layer comprises the following steps:
and (2) placing the CGO electrolyte powder in a 75-90 ℃ oven overnight, weighing a certain amount of components, pressing the components into an electrolyte layer green blank with a preset thickness under the conditions of 20-30MPa and 12-20min, and calcining the green blank at 1100-1500 ℃ for 2.5-4h to obtain the electrolyte layer.
Further, the preparation method of the CGO electrolyte powder comprises the following steps:
accurately weighing cerium nitrate hexahydrate (Ce (NO) according to the stoichiometric ratio of CGO 3 ) 3 ·6H 2 O), gadolinium oxide (Gd) 2 O 3 ) And Citric Acid (CA) as a starting material; first, gd is dissolved in dilute nitric acid 2 O 3 A powder; then, mixing the solutions, and adjusting the pH value of the mixed solution by using ammonia water until the solution is neutral; heating and stirring the mixed solution at 40-50 ℃ for 8-12h to form gel; heating the gel in an electric furnace to form light yellow powder; and finally, preserving the prepared powder at 550-700 ℃ for 0.5-1.5h, taking out the powder, and calcining the powder at 700-800 ℃ for 1-3h to obtain the CGO electrolyte powder.
Further, the preparation method of the cathode layer comprises the following steps:
uniformly mixing the Ni/CGO composite nano-fiber prepared by electrospinning and terpineol according to a preset proportion to prepare anode slurry, preparing a cathode layer with a preset thickness on one side of an electrolyte layer by a screen printing method, drying, and calcining for 1-3h at 800-1000 ℃.
Further, the preparation method of the anode layer comprises the following steps:
according to the mass ratio of 1:1, weighing LSM powder and CGO electrolyte powder, adding absolute ethyl alcohol into the mixed powder, fully ball-milling and drying, then uniformly mixing with terpineol according to a certain proportion to prepare anode slurry, preparing an anode layer on the other layer of the electrolyte layer by screen printing, drying and calcining for 0.8-3h at 900-1200 ℃.
Compared with the prior art, the CGO electrolyte matrix MS-SOEC structure provided by the invention has the advantages that the CGO electrolyte matrix MS-SOEC structure is supported by metal, the basic cathode, the anode and the electrolyte functional layer have certain thicknesses to ensure the smooth and continuous reaction of each part of the electrolytic cell, and the integral mechanical strength is ensured by the metal support body on the outer side of the cathode. The SOEC electrolysis water vapor reaction is the reverse of the hydrogen-oxygen type fuel cell reaction. When the CGO electrolyte base MS-SOEC is electrified and electrolyzed, H 2 O is introduced into the SOEC from the cathode flow channel and then diffused to the vicinity of a three-phase interface near the cathode and the electrolyte from the porous cathode to obtain electrons which are decomposed into H 2 And O 2- Generation of H 2 Escape from the hydrogen electrode; o is 2- Then the three-phase interface near the anode and the electrolyte is reached through the dense solid oxide electrolyte layer and loses electrons to generate O 2 And then diffuse out of the SOEC through the porous anode. The invention has the following advantages: 1) The metal support type solid oxide fuel electrolytic cell with the CGO electrolyte thickness of 15.1um is adopted, so that the purpose of running the solid oxide fuel electrolytic cell at the medium and low temperature can be realized, the running cost of the SOEC is reduced, and the industrial development of the SOEC is realized. 2) At different operating temperatures, the input voltage of the CGO electrolyte based MS-SOEC is equal to the input voltage of the three-layer electrolyte based MS-SOEC when a certain current density is reached.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the disclosure, nor is it intended to be used to limit the scope of the disclosure.
Drawings
The foregoing and other objects, features and advantages of the disclosure will be apparent from the following more particular descriptions of exemplary embodiments of the disclosure as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the disclosure.
FIG. 1 shows a working schematic of a CGO electrolyte based MS-SOEC structure of an embodiment of the invention;
FIG. 2 is a comparative schematic diagram showing the performance of a cell simulated by a CGO electrolyte-based MS-SOEC structure according to an embodiment of the invention
FIG. 3 shows a comparative schematic of experimental data for a simulated cell of a CGO electrolyte-based MS-SOEC structure of an embodiment of the invention;
fig. 4 is a graph showing experimental results of the operation of the CGO electrolyte-based MS-SOEC structure of the example of the present invention and the conventional three-layer electrolyte-based MS-SOEC.
Detailed Description
Embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The term "including" and variations thereof as used herein is intended to be open-ended, i.e., "including but not limited to". The term "or" means "and/or" unless specifically stated otherwise. The term "based on" means "based at least in part on". The terms "one example embodiment" and "one embodiment" mean "at least one example embodiment". The term "another embodiment" means "at least one additional embodiment". The terms "first," "second," and the like may refer to different or the same objects. Other explicit and implicit definitions are also possible below.
The embodiment provides a CGO electrolyte-based MS-SOEC structure, which includes a metal substrate, a cathode layer, an electrolyte layer, and an anode layer, wherein the cathode layer is deposited on an upper surface of the metal substrate, the electrolyte layer is deposited on the cathode layer, the electrolyte layer overlaps with the cathode layer, and the anode layer is deposited on the electrolyte layer.
Specifically, the metal substrate of the present embodiment is a steel substrate, and the steel substrate has a thickness of 200-
300um porous foil, with a set of small holes of 10-30um diameter formed in its central region by laser drilling. The peripheral length of the foil is not drilled and is used to seal the stack by welding, brazing or compression gaskets. A cathode layer is deposited on the upper surface of the substrate. The cathode is typically a porous nickel-CGO composite ceramic, about 15um thick. The electrolyte layer is deposited on the cathode to form a 10-15um CGO film. The electrolyte overlaps the cathode to seal the edges of the cathode. The CGO electrolyte based MS-SOEC in this example was set to a metal supported solid oxide fuel cell with a total electrolyte thickness of 15.1 um. Finally, an anode layer is deposited on top of the electrolyte to a thickness of about 25um.
The embodiment also provides a preparation method of the CGO electrolyte matrix MS-SOEC structure, which comprises the following steps:
the preparation method of the electrolyte layer comprises the following steps:
and (2) placing the CGO electrolyte powder in a 75-90 ℃ oven overnight, weighing a certain amount of components, pressing the components into an electrolyte layer green blank with a preset thickness under the conditions of 20-30MPa and 12-20min, and calcining the green blank at 1100-1500 ℃ for 2.5-4h to obtain the electrolyte layer.
Specifically, CGO electrolyte powder is put in an oven at 80 ℃ overnight, a certain amount of components are weighed, an electrolyte layer green body with the thickness of 15.1um is pressed under the conditions of 25MPa and 15min, and the green body is calcined at 1200 ℃ for 3h to obtain the electrolyte layer.
The preparation method of the CGO electrolyte powder comprises the following steps:
accurately weighing cerium nitrate hexahydrate (Ce (NO) according to the stoichiometric ratio of CGO 3 ) 3 ·6H 2 O), gadolinium oxide (Gd) 2 O 3 ) And Citric Acid (CA) as starting materials; first, gd is dissolved in dilute nitric acid 2 O 3 A powder; then, mixing the solutions, and adjusting the pH value of the mixed solution by using ammonia water until the solution is neutral; heating and stirring the mixed solution at 40-50 ℃ for 8-12h to form gel; heating the gel in an electric furnace to form light yellow powder; and finally, preserving the heat of the prepared powder at 550-700 ℃ for 0.5-1.5h, and then taking out the powder to be calcined at 700-800 ℃ for 1-3h to obtain the CGO electrolyte powder.
Specifically, CGO electrolyte powder and cerium nitrate hexahydrate (Ce(NO 3 ) 3 ·6H 2 O), gadolinium oxide (Gd) 2 O 3 ) And Citric Acid (CA) as a starting material. The raw materials are accurately weighed according to the stoichiometric ratio of CGO. First, gd is dissolved in dilute nitric acid 2 O 3 And (3) powder. Then, the above solutions were mixed, and Ph of the mixed solution was adjusted using ammonia water until the solution was neutral. The mixed solution was heated and stirred at 45 ℃ for 10 hours to form a gel. The gel was heated in an electric furnace to form a pale yellow powder. And finally, preserving the prepared powder for 1h at 600 ℃, and then taking out the powder to be calcined for 2h at 750 ℃ to obtain the CGO electrolyte powder.
Further, the preparation method of the cathode layer comprises the following steps:
uniformly mixing the Ni/CGO composite nano-fiber prepared by electrospinning and terpineol according to a preset proportion to prepare anode slurry, preparing a cathode layer with a preset thickness on one side of an electrolyte layer by a screen printing method, drying, and calcining for 1-3h at 800-1000 ℃.
Specifically, uniformly mixing the Ni/CGO composite nano-fiber prepared by electrospinning and terpineol according to a certain proportion to prepare anode slurry. A cathode having a thickness of 15um was prepared on the electrolyte layer side by a screen printing method, dried and then calcined at 900 ℃ for 2 hours.
Further, the preparation method of the anode layer comprises the following steps:
according to the mass ratio of 1:1, weighing LSM powder and CGO electrolyte powder, adding absolute ethyl alcohol into the mixed powder, fully ball-milling and drying the mixture, then uniformly mixing the mixture with terpineol according to a certain proportion to prepare anode slurry, preparing an anode layer on the other layer of the electrolyte layer by screen printing, drying the anode layer, and calcining the anode layer for 0.8 to 3 hours at the temperature of 900 to 1200 ℃.
Specifically, the mass ratio of 1:1, weighing LSM (solid oxide fuel cell cathode material) powder and CGO powder, adding absolute ethyl alcohol into the mixed powder, fully ball-milling and drying the powder, and then uniformly mixing the powder and terpineol according to a certain proportion to prepare anode slurry. And preparing an anode on the other layer of the electrolyte layer by screen printing, drying, and calcining at 1000 ℃ for 2h to obtain a single cell.
The working principle of the CGO electrolyte-based MS-SOEC structure of this example is as follows (refer to fig. 1):
when the CGO electrolyte base MS-SOEC is electrified and electrolyzed, H 2 O is introduced into the SOEC from the cathode flow channel and then diffused to the vicinity of a three-phase interface near the cathode and the electrolyte from the porous cathode to obtain electrons which are decomposed into H 2 And O 2- Generation of H 2 Escape from the hydrogen electrode; o is 2- Then the three-phase interface near the anode and the electrolyte is reached through the dense solid oxide electrolyte layer and loses electrons to generate O 2 And then diffuse out of the SOEC through the porous anode.
The CGO electrolyte-based MS-SOEC structure of this example was subjected to an experiment simulating the performance of a battery as follows:
the experimental conditions are as follows: the aperture, the substrate thickness, the anode thickness, the cathode thickness and the electrolyte thickness are respectively 100um, 150um, 15um, 25um and 15.1um CGO electrolyte-based metal-supported electrolytic cells; power supply voltage, a circulating water circuit, a gas circuit, a heater and the like.
The experimental process comprises the following steps: the operation temperature is 600 ℃; the operating pressure is 1atm; the operating current densities were 0A/m 2, 400A/m 2, 1700A/m 2, 2800A/m 2, 3800A/m 2, 5000A/m 2, 6000A/m 2, 7000A/m 2, 8000A/m 2, and 9000A/m 2, respectively.
The experimental results are as follows: the schematic diagram of the performance of the cell simulated by the CGO electrolyte-based MS-SOEC structure is shown in FIG. 2, the schematic diagram of the experimental data is shown in FIG. 3, the square curve and the circular curve in FIG. 2 and FIG. 3 respectively represent the experimental result and the simulation result, and the difference between the two results under the same operating condition and the corresponding current density is less than 5%, so that the accuracy requirement is met. It can be seen from the figure that in the open circuit condition, the potential is at a maximum, reaching the open circuit voltage, and as the current density increases, the polarization loss in cell operation increases and the potential decreases. When the current density was 9000A/m 2, the potential was close to 0, indicating that the cell could not be operated at an excessive current density.
The working process of the CGO electrolyte-based MS-SOEC structure of this example is as follows:
the cell operates under steady state conditions, the cell elements are constant at corresponding temperatures throughout, the porous electrode is composed of three homogeneous components, the gas volume fraction and pressure on the anode and cathode surfaces remain constant, and a standard Bulter-Volmer electrochemical power process is established. The invention also incorporates the electron conductivity of the CGO into the calculation of the potential, i.e. the electron potential of the anode and cathode is no longer constant but changes due to the effect of the electron resistance at different positions of the electrodes. In general, physical processes such as electron, ion conduction, and gas transport of porous electrodes need to be considered in the calculation process. The electron and ion transmission exists in the whole modeling area, and is used for calculating the electron and ion potentials of different positions of the battery and closely related to parameters such as electron conductivity and ion conductivity. The gas transport process is used to calculate the concentration of the component gases at different locations under cell operation, only in the porous anode and cathode structures.
The experiments performed on the CGO electrolyte-based MS-SOEC structure of this example and the existing three-layer electrolyte-based MS-SOEC were as follows:
the operating temperatures were set to 550 deg.C, 600 deg.C, 650 deg.C and 700 deg.C, respectively. The current density value of the batteries is 0A/m respectively at different operating temperatures 2 、400 A/m 2 、1700 A/m 2 、2800 A/m 2 、3800 A/m 2 、5000 A/m 2 、6000 A/m 2 、7000 A/m 2 、8000 A/m 2 、9000 A/m 2 As the operating point, the input voltage of the cell at that time was recorded.
The operation mode is as follows: the low current density is set to 0A/m 2 、400 A/m 2 、1700 A/m 2 、2800 A/m 2 、3800 A/m 2 、5000 A/m 2 (ii) a The high current density was set to 6000A/m 2 、7000 A/m 2 、8000 A/m 2 、9000 A/m 2 . Because the CGO can generate the electron leakage phenomenon when being used as the MS-SOEC electrolyte, but the electron leakage amount is negligible under the large current density, the two operation modes of the CGO electrolyte-based MS-SOEC and the existing three-layer electrolyte-based MS-SOEC under the small current density and the large current density are respectively set in this embodiment, and the input voltages required by the operation of the two modes are compared.
The results of the experiment are shown in FIG. 4, and can be seen from FIG. 4It is seen that both show an increasing trend with increasing current density. When the electrolytic cell operates at a medium-low temperature of 550-650 ℃, the output voltage of the three-layer electrolyte matrix MS-SOEC is obviously lower than that of the CGO electrolyte MS-SOEC under a low current density; as the current density increases, the output voltages of the two become gradually equal. When the electrolytic cell operates at a medium-high temperature of 700 ℃, the output voltage of the three-layer electrolyte matrix MS-SOEC is always lower than that of the CGO electrolyte matrix; however, as the current density increased, the two became equal, at 9000A/m 2 When the output voltages are equal, the output voltages are equal. Considering that the electrolytic cell preferably produces a large amount of hydrogen under high current, and considering the manufacturing cost of the three-layer electrolyte-based MS-SOEC, the integration of the electrolytic cell system and the like, the CGO-based MS-SOEC is selected to have better hydrogen production effect under high current density.
In summary, in the CGO electrolyte based MS-SOEC structure of the present embodiment, the CGO electrolyte based MS-SOEC structure is a metal support, the basic cathode, anode and electrolyte functional layer all have a certain thickness to ensure the smooth and continuous reaction of each part of the electrolytic cell, and the overall mechanical strength is ensured by the metal support outside the cathode. The SOEC electrolysis water vapor reaction is the reverse of the hydrogen-oxygen type fuel cell reaction. When the CGO electrolyte base MS-SOEC is electrified and electrolyzed, H 2 O is introduced into the SOEC from the cathode flow channel and then diffused to the vicinity of a three-phase interface near the cathode and the electrolyte from the porous cathode to obtain electrons which are decomposed into H 2 And O 2- Generation of H 2 Escape from the hydrogen electrode; o is 2- The electrons are lost to form O through the dense solid oxide electrolyte layer to the three-phase interface between the anode and the electrolyte 2 And then diffuse out of the SOEC through the porous anode. The invention has the following advantages: 1) The metal support type solid oxide fuel electrolytic cell with the CGO electrolyte thickness of 15.1um is adopted, so that the purpose of running the solid oxide fuel electrolytic cell at the medium and low temperature can be realized, the running cost of the SOEC is reduced, and the SOEC industrialized development is realized. 2) At different operating temperatures, the input voltage of the CGO electrolyte based MS-SOEC is equal to the input voltage of the three layer electrolyte based MS-SOEC when a certain current density is reached.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terms used herein were chosen in order to best explain the principles of the embodiments, the practical application, or technical improvements to the techniques in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims (4)

1. A preparation method of a CGO electrolyte-based MS-SOEC structure is characterized in that the CGO electrolyte-based MS-SOEC structure comprises the following steps: the cathode layer is deposited on the upper surface of the metal substrate, the electrolyte layer is deposited on the cathode layer, the electrolyte layer is overlapped with the cathode layer, and the anode layer is deposited on the electrolyte layer;
the preparation method of the electrolyte layer comprises the following steps:
placing CGO electrolyte powder in a baking oven at 75-90 ℃ overnight, weighing a certain amount of components, pressing the components under 20-30MPa for 12-20min to obtain an electrolyte layer green compact with a predetermined thickness, and calcining the green compact at 1100-1500 ℃ for 2.5-4h to obtain an electrolyte layer;
the preparation method of the cathode layer comprises the following steps:
uniformly mixing the Ni/CGO composite nano-fiber prepared by electrospinning and terpineol according to a preset proportion to prepare cathode slurry, preparing a cathode layer with a preset thickness on one side of an electrolyte layer by a screen printing method, drying, and calcining at 800-1000 ℃ for 1-3h;
the preparation method of the anode layer comprises the following steps:
according to the mass ratio of 1:1, weighing LSM powder and CGO electrolyte powder, adding absolute ethyl alcohol into the mixed powder, fully ball-milling and drying the mixture, then uniformly mixing the mixture with terpineol according to a certain proportion to prepare anode slurry, preparing an anode layer on the other layer of the electrolyte layer by screen printing, drying the anode layer, and calcining the anode layer for 0.8 to 3 hours at the temperature of 900 to 1200 ℃.
2. The method of preparing the CGO electrolyte-based MS-SOEC structure of claim 1, wherein the method of preparing the CGO electrolyte powder comprises the steps of:
accurately weighing cerium nitrate hexahydrate (Ce (NO) according to the stoichiometric ratio of CGO 3 ) 3 ·6H 2 O), gadolinium oxide (Gd) 2 O 3 ) And Citric Acid (CA) as starting materials; first, gd is dissolved in dilute nitric acid 2 O 3 A powder; then, mixing the solutions, and adjusting the pH value of the mixed solution by using ammonia water until the solution is neutral; heating and stirring the mixed solution at 40-50 ℃ for 8-12h to form gel; heating the gel in an electric furnace to form light yellow powder; and finally, preserving the prepared powder at 550-700 ℃ for 0.5-1.5h, taking out the powder, and calcining the powder at 700-800 ℃ for 1-3h to obtain the CGO electrolyte powder.
3. The method of making a CGO electrolyte-based MS-SOEC structure according to claim 1, wherein the central region of the metal substrate is drilled with a number of bores.
4. The method of preparing a CGO electrolyte-based MS-SOEC structure according to claim 3, wherein the diameter of the drilled hole is 10-30um.
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