CN115775902A - Method for improving density of electrolyte layer of fuel cell and fuel cell - Google Patents
Method for improving density of electrolyte layer of fuel cell and fuel cell Download PDFInfo
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- CN115775902A CN115775902A CN202211641934.4A CN202211641934A CN115775902A CN 115775902 A CN115775902 A CN 115775902A CN 202211641934 A CN202211641934 A CN 202211641934A CN 115775902 A CN115775902 A CN 115775902A
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Classifications
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- 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
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- Fuel Cell (AREA)
Abstract
The invention discloses a method for improving the density of an electrolyte layer of a fuel cell and the fuel cell, wherein the method for improving the density of the electrolyte layer of the fuel cell comprises the following steps: providing a metal support; forming a cathode layer on one surface of the metal support: forming a first electrolyte layer with the porosity of 5-10% on the surface of one side, away from the metal support, of the cathode layer; and enabling the surface of the first electrolyte layer far away from the metal support body to be in contact with molten metal, and enabling the molten metal to generate electrochemical oxidation reaction in the holes of the first electrolyte layer through an external power supply so as to obtain the electrolyte layer. The electrolyte layer prepared by the method has high density and good stability, and can effectively reduce the internal resistance of the fuel cell.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a method for improving the density of an electrolyte layer of a fuel cell and the fuel cell.
Background
The metal-supported solid oxide fuel cell can improve the mechanical strength of the cell, increase the thermal shock resistance of the cell and reduce the system cost, so the metal-supported solid oxide fuel cell gradually becomes a new research point in the field of fuel cells in recent years. The electrolyte layer of the metal support fuel cell is prepared by utilizing the plasma spraying technology, the cell does not need to be sintered at high temperature for a long time, the problems of electrode chromium poison, high-temperature oxidation of a metal support body and the like caused by high-temperature sintering of the electrolyte in the preparation process of the traditional sintering method can be avoided, and the electrolyte layer prepared at present is not compact enough.
Therefore, there is still a need for improvements in the methods and fuel cells for increasing the density of the electrolyte layer of the fuel cell.
Disclosure of Invention
The present invention is made based on the findings of the inventors on the following problems:
the inventor finds that although the cost of preparing the electrolyte layer by using the atmospheric plasma spraying technology is low, the prepared electrolyte layer has poor compactness, and gas leakage at two sides of the electrodes of the cathode layer and the anode layer of the fuel cell is caused, so that the partial pressure of the gas of the cathode layer and the gas of the anode layer are reduced, the open-circuit voltage of the fuel cell is reduced, and therefore, the densification operation of the electrolyte layer is required to be further performed to improve the compactness. The inventors have further found that the treatment of the electrolyte layer by the impregnation method in the related art, although it is possible to reduce the porosity of the electrolyte layer, requires a plurality of impregnation processes, takes a long process flow, and has difficulty in eliminating the contact resistance of the electrolyte layer; in the related art, a low-melting-point electrolyte compounding method is adopted, for example, antimony oxide and bismuth oxide are adopted to form an electrolyte layer together, and the electrolyte layer is easily reduced into a metal simple substance during the operation of a fuel cell, so that the cell is short-circuited and fails.
The present invention aims to alleviate or solve at least to some extent at least one of the above mentioned problems.
In one aspect of the invention, the invention provides a method for improving the compactness of an electrolyte layer of a fuel cell, which comprises the following steps: providing a metal support; forming a cathode layer on one surface of the metal support: forming a first electrolyte layer with the porosity of 5-10% on the surface of one side, away from the metal support, of the cathode layer; and contacting the surface of the first electrolyte layer far away from the metal support body with molten metal, and enabling the molten metal to generate electrochemical oxidation reaction in the holes of the first electrolyte layer through an external power supply so as to obtain the electrolyte layer. Therefore, the electrolyte layer with high density and good stability can be obtained.
According to an embodiment of the invention, the molten metal comprises at least one of the metals aluminium, sodium, potassium and gallium. Therefore, the adopted metal has stable property, the oxide is not easy to be reduced, and the safety performance of the fuel cell is improved.
According to an embodiment of the invention, the method further comprises: the surface of the metal support body with the first electrolyte layer is placed upwards, and a molten pool is arranged on the surface of the first electrolyte layer far away from the metal support body, and molten metal is contained in the molten pool. This can further increase the density of the electrolyte layer.
According to an embodiment of the present invention, the difference between the temperature of the molten metal and the melting point of the molten metal is not less than 50 ℃. This promotes melting of the molten metal, and the density of the electrolyte layer can be further improved.
According to an embodiment of the invention, the melting of the molten metal is performed under an inert gas. Therefore, the oxidation of metal in the melting process can be reduced, and the compactness of the electrolyte layer can be further improved.
According to an embodiment of the invention, the level of the molten metal in the molten bath is at least 2cm. This can further increase the density of the electrolyte layer.
According to the embodiment of the invention, one end of the external power supply is electrically connected with the molten metal, and the other end of the external power supply is electrically connected with the metal support. Therefore, in-situ electrochemical oxidation of the molten metal in the first electrolyte layer hole can be generated, and the compactness of the electrolyte layer is further improved.
According to an embodiment of the invention, the current density of the electrochemical oxidation reaction is between 0.01 and 0.05A/cm 2 . Therefore, the electrolyte layer with high density and good stability can be obtained.
According to an embodiment of the invention, the method further comprises: and forming a molten metal oxide layer on the surface of the electrolyte layer, and removing the molten metal oxide layer. This makes it possible to obtain an electrolyte layer having high density.
In another aspect of the present invention, the present invention provides a fuel cell comprising the electrolyte layer prepared by the method described above. Thus, the battery has all the features and advantages of the electrolyte layer, which will not be described herein.
Drawings
FIG. 1 is a flow chart of a method of densifying an electrolyte layer of a fuel cell according to an embodiment of the present invention;
fig. 2 is a schematic view of a partial structure of a fuel cell according to an embodiment of the present invention;
FIG. 3 is a schematic view of an electrochemical oxidation reaction apparatus according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a fuel cell partial structure after completion of an electrochemical oxidation reaction according to one embodiment of the present invention;
FIG. 5 is a schematic diagram of a fuel cell configuration according to one embodiment of the present invention;
fig. 6 is a scanning electron microscope photograph of the electrolyte layer of example 1 of the present invention.
Reference numerals:
a metal support body: 10; a cathode layer: 20; a first electrolyte layer: 30, of a nitrogen-containing gas; first electrolyte layer pore: 310; molten metal: 40; molten metal oxide layer: 50; molten metal oxide: 320, a first step of mixing; molten pool: 70; an electrolyte layer: 80; anode layer: 90.
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present application and are not to be construed as limiting the present application.
In one aspect of the present invention, the present invention provides a method for improving the density of an electrolyte of a fuel cell, and in particular, referring to fig. 1, the method may include the following steps:
s100, providing a metal support
According to some embodiments of the present invention, the metal support is the most basic feature of the metal-supported solid oxide fuel cell compared to the conventional solid oxide fuel cell, the metal support has a higher thermal conductivity, which can greatly reduce the thermal gradient and the thermal stress of the solid oxide fuel cell, and the metal support also has a higher electrical conductivity, which can improve the electrical performance of the solid oxide fuel cell. The process for preparing the metal support is not particularly limited, and for example, the metal support can be obtained by processes such as thin plate laser processing, chemical etching, and powder metallurgy.
According to some embodiments of the present invention, the material of the metal support is not particularly limited, for example, the material of the metal support may be a stainless steel material, which may better support the cathode layer and the electrolyte layer above the metal support due to better oxidation resistance and long-term stability.
According to some embodiments of the present invention, since the solid oxide fuel cell requires an atmosphere to be introduced during operation, the metal support may have a porosity, and the porosity of the metal support is not particularly limited, and may be, for example, 15 to 30%.
According to some embodiments of the present invention, the thickness of the metal support is not particularly limited, for example, the thickness of the metal support may be 0.5 to 3mm, and when the thickness of the metal support is greater than 0.5mm, the cathode layer, the electrolyte layer, and the anode layer thereon can be effectively supported.
S200: forming a cathode layer on one side surface of the metal support
According to some embodiments of the present invention, the cathode layer is disposed on a side surface of the metal support, and the cathode layer serves as a cathode of the metal-air battery in a subsequent electrochemical oxidation process, and a cathode reaction is generated at the cathode, where oxygen is obtained from electrons to generate oxygen ions, and specifically, a preparation process of the cathode layer is not particularly limited, for example, the cathode layer may be obtained by an atmospheric plasma spraying process, that is, a powder supply system is used to send cathode layer material powder into a core of a high-temperature and high-speed plasma flame generated by a spray gun, the powder may be rapidly changed into molten droplets and accelerated under the action of the high-temperature and high-speed flame, and finally the molten droplets may collide with the metal support to be cooled and solidified, and the molten droplets are continuously deposited on the metal support to form the cathode layer, and the cathode layer obtained by the plasma spraying process may reduce an interface reaction between the metal support material and the cathode layer material, and improve a binding force between the cathode layer and the metal support.
According to some embodiments of the present invention, the first arc power for spraying the cathode layer by using the atmospheric plasma spraying process is not particularly limited, for example, the first arc power may be 25 to 35kW, and when the first arc power may be 25 to 35kW, the porosity of the cathode layer can be increased, which is beneficial for gas to diffuse and migrate in pores during the subsequent electrochemical oxidation process, thereby promoting the subsequent electrochemical oxidation reaction, and thus obtaining the electrolyte layer with higher compactness.
According to some embodiments of the present invention, the porosity of the cathode layer is not particularly limited, for example, the porosity may be 20 to 30%. When the porosity of the cathode layer is less than 20%, effective gas diffusion and migration channels of the cathode layer are reduced, so that subsequent electrochemical oxidation reaction is not facilitated, and the density of the electrolyte layer is further influenced; when the porosity of the cathode layer is more than 30%, the effective conductive volume of the cathode layer is reduced, so that the working voltage of the solid oxide fuel cell is influenced; when the porosity of the cathode layer is 20-30%, gas can be favorably diffused and migrated in the pores of the cathode layer, and then the subsequent in-situ electrochemical oxidation reaction can be promoted to occur.
S300: forming a first electrolyte layer on the surface of the cathode layer far away from the metal support
According to some embodiments of the present invention, the electrolyte layer in the solid fuel cell acts as a barrier to oxygen and fuel, and when the electrolyte layer is less dense, gas leakage is caused on both sides of the cathode layer and anode layer of the fuel cell, so that the partial pressure of the gas on the cathode layer and anode layer is reduced, thereby reducing the open-circuit voltage of the fuel cell. In this step, a first electrolyte layer with a porosity of 5-10% is formed on a surface of the cathode layer away from the metal support, and then an electrolyte layer with a higher density is formed by performing densification treatment on the first electrolyte layer, referring to fig. 2, a cathode layer 20 is formed on a surface of the metal support 10, and a first electrolyte layer 30 is formed on a surface of the cathode layer away from the metal support 10, where the first electrolyte layer 30 has pores 310.
According to some embodiments of the present invention, the process for preparing the first electrolyte layer is not particularly limited, for example, the first electrolyte layer may be obtained by an atmospheric plasma spraying process, and the first electrolyte layer obtained by the foregoing process can reduce the interface reaction between the first electrolyte layer material and the cathode layer material and improve the binding force between the cathode layer and the first electrolyte layer.
According to some embodiments of the present invention, the second arc power for spraying the first electrolyte layer by the atmospheric plasma spraying process is not particularly limited, for example, the second arc power may be 45 to 50kW, and when the second arc power may be 45 to 50kW, the melting degree of the powder material of the first electrolyte layer during the spraying process can be increased, and after the first electrolyte layer powder droplet with better melting degree is deposited on the surface of the cathode layer, the first electrolyte layer with lower porosity can be formed, that is, the porosity of the first electrolyte layer sprayed by the second arc power is 5 to 10%.
S400: the surface of the first electrolyte layer, which is far away from the metal support body, is contacted with the molten metal, and the molten metal is subjected to electrochemical oxidation reaction in the holes of the first electrolyte layer through an external power supply.
According to some embodiments of the present invention, in this step, a surface of the first electrolyte layer away from the metal support is contacted with the molten metal, that is, the surface of the first electrolyte layer away from the metal support serves as a bottom surface of the molten pool, and the molten metal is subjected to an electrochemical oxidation reaction in the pores of the first electrolyte layer by an external power supply, so that the molten metal is oxidized into a metal oxide in the pores of the first electrolyte layer and undergoes volume expansion, thereby achieving effective filling in the pores of the first electrolyte layer.
According to some embodiments of the present invention, the material of the molten metal is not particularly limited, for example, the material of the molten metal may include at least one of the metals aluminum, sodium, potassium, and gallium. The lower melting points of the metals aluminum, sodium, potassium and gallium facilitate melting of the metals at lower temperatures, whereby the electrochemical oxidation reaction can be performed at lower temperatures, and the oxides of the foregoing metals are less likely to be reduced to metals by hydrogen, and the metal oxides of the foregoing metals can be stably present in the pores of the first electrolyte layer during the operation of the fuel cell.
According to some embodiments of the invention, the metal support may be placed with the first electrolyte layer surface facing upwards in this step, and a molten pool with molten metal therein may be provided on a surface of the first electrolyte layer remote from the metal support. Referring to fig. 3, a molten pool 70 may be provided on a surface of the first electrolyte layer 30 on a side remote from the metal support 10, the molten pool 70 being internally filled with the molten metal 40.
According to some embodiments of the present invention, the molten pool is disposed on a side surface of the first electrolyte layer away from the metal support, so as to reduce overflow of the molten metal on the surface of the first electrolyte layer, and the material of the molten pool is not particularly limited, for example, the material of the molten pool may be quartz, corundum, etc., and when the material of the molten pool is quartz or corundum, the material of the molten pool does not react with the molten metal material during the metal melting and electrochemical oxidation reaction.
According to some embodiments of the present invention, the difference between the temperature of the molten metal and the melting point of the molten metal may be not less than 50 ℃, and when the difference between the temperature of the molten metal and the melting point of the molten metal is not less than 50 ℃, the metal can be better melted to enter the pores of the first electrolyte layer for oxidation reaction, so as to achieve effective filling of the pores of the first electrolyte layer, for example, the melting point of aluminum is 660 ℃, and the corresponding temperature of the molten aluminum is at least 710 ℃.
According to some embodiments of the present invention, the melting process of the metal is performed under an inert gas, the inert gas may be at least one selected from nitrogen, helium, neon, argon, krypton, xenon, and radon, and the inert gas has a stable chemical property, and can provide a good protection effect for the metal during the melting process of the metal to prevent the metal from being oxidized.
According to some embodiments of the present invention, the amount of the metal added is not particularly limited, for example, the amount of the metal added may be such that the height of the molten metal level in the molten pool after the metal is melted is not less than 2cm, and when the height of the molten metal level in the molten pool is not less than 2cm, a sufficient amount of the molten metal can enter the pores of the first electrolyte layer and an oxidation reaction can occur, so that the pores of the first electrolyte layer can be effectively filled.
According to some embodiments of the present invention, the external power source is not particularly limited, for example, one end of the external power source may be electrically connected to the molten metal, and the other end of the external power source may be electrically connected to the metal support, and specifically, referring to fig. 3, the positive electrode of the external power source 60 is connected to the metal support 10 through a metal wire, and the negative electrode of the external power source 60 is connected to the molten metal 40 through a graphite rod embedded in the molten metal 40 in advance, so that the molten metal and air form a molten metal-air battery, and when the power source is discharged, a cathode reaction occurs at the interface between the cathode layer 20 and the first electrolyte layer 30, an anode reaction occurs at the interface between the first electrolyte layer pores 310 and the interface between the first electrolyte layer 30 and the molten metal 40, and thus the densification process of the first electrolyte is completed.
According to some embodiments of the present invention, the electrochemical oxidation reaction of the molten metal in the pores of the first electrolyte layer is performed by an external power source, and specifically, the cathode reaction is performed by an external power source to generate oxygen at the interface of the cathode layer and the first electrolyte layer to generate electrons and generate oxygen ionsI.e. O 2 +4e - →2O 2- And carrying out anode reaction in pores of the first electrolyte layer and at the interface of the first electrolyte layer and the molten metal, so that the molten metal loses electrons and is combined with oxygen ions to generate metal oxide, thereby realizing electrochemical oxidation of the molten metal. Taking metallic aluminum as an example, the molten metallic aluminum is subjected to an anodic reaction in the pores of the first electrolyte layer and at the interface between the first electrolyte layer and the molten metallic aluminum, and the aluminum loses electrons, i.e. 2Al-6e - +3O 2- →Al 2 O 3 。
According to some embodiments of the present invention, oxygen ions diffuse and migrate in the first electrolyte layer, and the liquid metal that preferentially permeates into the pores of the first electrolyte layer is oxidized and undergoes volume expansion, so that the pores of the first electrolyte layer are effectively filled to form a high-density and high-stability electrolyte layer.
According to some embodiments of the present invention, the current density of the electrochemical oxidation reaction is not particularly limited, for example, the current density may be 0.01 to 0.05A/cm 2 When the current density is 0.01-0.05A/cm 2 And meanwhile, the electrochemical oxidation reaction is facilitated to be stably carried out, the electrochemical oxidation reaction of the molten metal in the pores of the first electrolyte layer is promoted, and the electrolyte layer with higher density is obtained.
According to some embodiments of the invention, the type of power source is not particularly limited, for example, the power source may include one of an electrochemical workstation and an electronic load.
According to some embodiments of the present invention, the above electrochemical oxidation reaction may be prolonged until a molten metal oxide layer is formed on the surface of the electrolyte layer, so as to ensure that the pores inside the electrolyte layer are filled with metal oxide, and the excess molten metal oxide layer is removed by subsequent processing, referring to fig. 4, the pores of the first electrolyte layer 30 are filled with molten metal oxide 320 to form a high-density electrolyte layer 80, when the molten metal oxide layer is formed on the surface of the electrolyte layer 80, the power supply stops working, the molten pool is removed from the surface of the electrolyte layer, and the surface of the electrolyte layer is polished by sand paper, so as to complete the densification process of the electrolyte layer. The method provided by the invention can be used for improving the density of the electrolyte layer of the fuel cell, so that the electrolyte layer with the density of more than 99% can be obtained, the electrolyte layer can meet the requirement of the fuel cell on the density of the electrolyte layer, and the internal resistance of the solid oxide fuel cell is effectively reduced. Specifically, the thickness of the molten metal oxide layer formed on the surface of the electrolyte layer is not particularly limited, and for example, the thickness of the oxide layer may be at least 1cm.
In another aspect of the present invention, the present invention also provides a fuel cell including the electrolyte layer prepared by the foregoing method, and thus having all the features and advantages of the electrolyte layer prepared by the foregoing method.
According to some embodiments of the present invention, the fuel cell includes a metal support, a cathode layer, an electrolyte layer, and an anode layer, referring to fig. 5, the cathode layer 20 is located on one side surface of the metal support 10, the electrolyte layer 80 is located on one side surface of the cathode layer 20 away from the metal support, and the anode layer 90 is located on one side surface of the electrolyte layer 80 away from the cathode layer 20, wherein the electrolyte layer 80 is prepared by the method described above.
According to some embodiments of the present invention, the preparation process of the anode layer is not particularly limited, and for example, the anode layer may be obtained by an atmospheric plasma spraying process, and the anode layer obtained by the foregoing process can reduce interfacial reaction between the anode layer material and the electrolyte layer material and improve the bonding force between the anode layer and the electrolyte layer.
According to some embodiments of the present invention, the anode layer and the cathode layer may be formed by one of magnetron sputtering, chemical vapor deposition, vacuum plasma spraying, supersonic flame spraying, and cold spraying.
The following describes in detail embodiments of the present invention. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
And spraying a cathode layer on the surface of the metal support body by adopting a plasma spraying process with first arc power of 30kW, and spraying a first electrolyte layer on the surface of the cathode layer by adopting a plasma spraying process with second arc power of 47 kW.
And placing the molten pool above the first electrolytic layer, filling metal aluminum powder into the molten pool, embedding a graphite rod into the aluminum powder, and connecting the molten pool with an electrochemical workstation externally, wherein the anode of the electrochemical workstation is connected with the stone grinding rod through a lead, and the cathode of the electrochemical workstation is connected with the metal support body through a lead. The molten pool, the first electrolyte layer, the cathode layer and the metal support are heated to 710 ℃ to completely melt and preserve the temperature of the aluminum powder. Electrochemical workstation at 0.03A/cm 2 Discharging the current density to enable the surface of the first electrolyte layer and pores to generate electrochemical oxidation reaction, stopping discharging when an alumina layer with the thickness of 1cm appears on the surface of the first electrolyte layer, removing a molten pool, and cleaning and polishing the surface of the electrolyte layer to obtain the electrolyte layer with higher density.
Examples 2-9, comparative examples 1-6 are the same process as example 1, except for the current density, type of metal, molten metal level and melting temperature, see table 1 for details.
TABLE 1
Full cells were assembled from the densified electrolyte layers of examples 1-9, and comparative examples 1-6, operated in a hydrogen atmosphere and tested, as detailed in table 2.
TABLE 2
From table 2 in combination with fig. 6, it can be concluded that the density of the electrolyte layer can be significantly improved by using the molten metal in-situ electrochemical oxidation scheme, and the open-circuit voltage of the cell can be significantly improved when hydrogen is used as a fuel.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may be directly contacting the second feature or the first and second features may be indirectly contacting each other through intervening media. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of increasing the density of an electrolyte layer of a fuel cell, comprising the steps of:
providing a metal support;
forming a cathode layer on one surface of the metal support:
forming a first electrolyte layer with the porosity of 5-10% on the surface of one side, away from the metal support, of the cathode layer;
and enabling the surface of the first electrolyte layer far away from the metal support body to be in contact with molten metal, and enabling the molten metal to generate electrochemical oxidation reaction in the holes of the first electrolyte layer through an external power supply so as to obtain the electrolyte layer.
2. The method of claim 1, wherein the molten metal comprises at least one of the metals aluminum, sodium, potassium, and gallium.
3. The method of claim 1, further comprising: the surface of the metal support body having the first electrolyte layer is placed face up and a molten pool having molten metal therein is provided on the surface of the first electrolyte layer on the side away from the metal support body.
4. The method of claim 3, wherein the temperature of the molten metal differs from the melting point of the molten metal by no less than 50 ℃.
5. The method of claim 4, wherein the melting of the molten metal is performed under an inert gas.
6. The method of claim 3, wherein the level of the molten metal in the molten bath is at least 2cm.
7. The method of claim 1, wherein one end of the external power source is electrically connected to the molten metal and the other end of the external power source is electrically connected to the metal support.
8. The method of claim 7, wherein the electrochemical oxidation reaction has a current density of 0.01 to 0.05A/cm 2 。
9. The method of claim 1, further comprising: forming a molten metal oxide layer on the surface of the electrolyte layer,
and removing the molten metal oxide layer.
10. A fuel cell comprising an electrolyte layer produced by the method according to any one of claims 1 to 9.
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