CN116914173A - Compact isolation layer, preparation method thereof and solid oxide fuel cell - Google Patents
Compact isolation layer, preparation method thereof and solid oxide fuel cell Download PDFInfo
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- CN116914173A CN116914173A CN202311138641.9A CN202311138641A CN116914173A CN 116914173 A CN116914173 A CN 116914173A CN 202311138641 A CN202311138641 A CN 202311138641A CN 116914173 A CN116914173 A CN 116914173A
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- 238000002955 isolation Methods 0.000 title claims abstract description 52
- 239000000446 fuel Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007787 solid Substances 0.000 title claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 98
- 239000000843 powder Substances 0.000 claims abstract description 60
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 claims abstract description 58
- 238000004070 electrodeposition Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 52
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 34
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 26
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 18
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000011698 potassium fluoride Substances 0.000 claims description 14
- 235000013024 sodium fluoride Nutrition 0.000 claims description 13
- 239000011775 sodium fluoride Substances 0.000 claims description 13
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 235000011164 potassium chloride Nutrition 0.000 claims description 11
- 239000001103 potassium chloride Substances 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 229910002086 ceria-stabilized zirconia Inorganic materials 0.000 claims description 10
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 10
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 10
- 235000003270 potassium fluoride Nutrition 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- QBYHSJRFOXINMH-UHFFFAOYSA-N [Co].[Sr].[La] Chemical compound [Co].[Sr].[La] QBYHSJRFOXINMH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- FFQALBCXGPYQGT-UHFFFAOYSA-N 2,4-difluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(F)C=C1F FFQALBCXGPYQGT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OYCWBLFDGYRWSR-UHFFFAOYSA-N [Co][Fe][Sr][La] Chemical compound [Co][Fe][Sr][La] OYCWBLFDGYRWSR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
- H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
-
- 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
-
- 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 application provides a compact isolation layer, a preparation method thereof and a solid oxide fuel cell, wherein the preparation method of the compact isolation layer comprises the following steps: preparing gadolinium-doped cerium oxide powder; preparing an electrodeposition electrolyte; mixing gadolinium-doped cerium oxide powder with an electrodeposition electrolyte to obtain a mixed electrolyte; and (3) placing the battery sample into the mixed electrolyte for electrodeposition to obtain a compact isolation layer. According to the technical scheme, the gadolinium-doped cerium oxide isolation layer is prepared by adopting molten salt electrochemical deposition, a compact isolation layer can be formed in molten salt without sintering, the process is simple, the compactness is good, and the performance of the fuel cell is improved.
Description
Technical Field
The application relates to the technical field of solid oxide fuel cells, in particular to a compact isolation layer, a preparation method thereof and a solid oxide fuel cell.
Background
The structure of a solid oxide fuel cell includes an anode, a cathode, and an electrolyte. In the high-temperature preparation and operation process of the battery, sr element of the cathode can diffuse into the electrolyte layer and chemically react with the electrolyte layer to generate a layer of compact oxide strontium zirconate with poor conductivity, so that the performance and stability of the battery are reduced. A common approach to solve this problem is to add a separator between the electrolyte and the cathode to block the reaction of the oxygen electrolyte with the cathode. Cerium oxide-based ceramic materials are typically made from trivalent rare earth doped cerium oxide materials, such as gadolinium doped cerium oxide (abbreviated GDC). Because of its stable chemical properties, it is not easy to react with perovskite cathode material, becoming the most commonly used isolating layer material at present.
The screen printing method is the most commonly used preparation method of the cerium oxide-based isolation layer at present, and has the characteristics of simplicity in operation, low cost, high preparation speed and the like. However, the silk-screened cerium oxide-based separator film is difficult to densify during sintering, and a porous structure is formed, and the separator of the porous structure cannot completely block the reaction of the electrolyte and the cathode. In addition, when the method is adopted, the yttria stabilized zirconia electrolyte and the GDC isolation layer are easy to mutually diffuse in the preparation process to generate the yttria stabilized zirconia-gadolinium doped ceria solid solution, and the conductivity of the yttria stabilized zirconia-gadolinium doped ceria solid solution is two orders of magnitude lower than that of the yttria stabilized zirconia at the same temperature, so that the performance of the fuel cell is reduced.
Disclosure of Invention
The present application aims to solve or improve the above technical problems.
To this end, a first object of the present application is to provide a process for the preparation of a dense isolating layer.
A second object of the present application is to provide a dense barrier layer.
A third object of the present application is to provide a solid oxide fuel cell.
In order to achieve the first object of the present application, a technical solution of the first aspect of the present application provides a method for preparing a dense isolation layer, including: preparing gadolinium-doped cerium oxide powder; preparing an electrodeposition electrolyte; mixing gadolinium-doped cerium oxide powder with an electrodeposition electrolyte to obtain a mixed electrolyte; and (3) placing the battery sample into the mixed electrolyte for electrodeposition to obtain a compact isolation layer.
According to the preparation method of the compact isolation layer provided by the application, gadolinium-doped cerium oxide powder and electrodeposition electrolyte are prepared first. And then mixing gadolinium-doped cerium oxide powder with the electrodeposition electrolyte to obtain a mixed electrolyte. And finally, placing the battery sample into the mixed electrolyte for electrodeposition to obtain a compact isolation layer. The gadolinium-doped cerium oxide isolation layer is prepared through fused salt electrochemical deposition, a compact isolation layer can be formed in fused salt without sintering, the process is simple, the compactness is good, the reaction of electrolyte and a cathode of a fuel cell can be blocked, and the performance of the fuel cell is improved.
In addition, the technical scheme provided by the application can also have the following additional technical characteristics:
in the technical scheme, the battery sample is put into the mixed electrolyte for electrodeposition to obtain the compact isolation layer, and the method specifically comprises the following steps of: placing a battery sample and a graphite plate into the mixed electrolyte, connecting the battery sample with an anode of a power supply, and connecting the graphite plate with a cathode of the power supply; the cell sample was subjected to a current density of 0.1A/dm at 800℃to 950 ℃ 2 -1A/dm 2 And depositing for 5-30 min to form a compact isolation layer on the surface of the electrolyte layer of the battery sample.
In the technical scheme, a battery sample is placed in a mixed electrolyte for electrodeposition to obtain a compact isolation layer, specifically, the battery sample is firstly placed in a container and connected with an anode of a power supply, and the other end of the power supply is connected with a graphite plate and placed in the container.And then electrodepositing the battery sample to obtain a compact isolation layer. Wherein the current density is 0.1A/dm 2 -1A/dm 2 Setting the temperature at 800-950 ℃ and depositing for 5-30 min. By electrodeposition, gadolinium-doped cerium oxide in the mixed electrolyte can adsorb to the electrolyte layer surface of the battery sample, thereby forming a dense separator layer.
In the technical scheme, the preparation method of the gadolinium-doped cerium oxide powder specifically comprises the following steps: mixing molten salt composed of sodium chloride, potassium chloride and lithium fluoride with powder composed of gadolinium nitrate and cerium oxide, placing the mixture in a closed tank body, sintering the mixture at 800-950 ℃, and preserving the temperature for 4-20 hours to obtain initial gadolinium-doped cerium oxide powder; cleaning and drying the initial gadolinium-doped cerium oxide powder to obtain gadolinium-doped cerium oxide powder; wherein, the mass ratio of the molten salt to the powder is 100:5 to 100: 60.
In the technical scheme, gadolinium-doped cerium oxide powder and electrodeposition electrolyte are prepared, specifically, molten salt composed of sodium chloride, potassium chloride and lithium fluoride is firstly mixed with powder composed of gadolinium nitrate and cerium oxide, and the mixture is placed in a closed tank body to be sintered at 800-950 ℃, and the temperature is kept for 4-20 hours, so that the initial gadolinium-doped cerium oxide powder is obtained. And then cleaning and drying the original gadolinium-doped cerium oxide powder to finish the preparation of the gadolinium-doped cerium oxide powder. Wherein, the molten salt component: powder = 100: 5-60.
In the technical scheme, the preparation method of the electrodeposition electrolyte specifically comprises the following steps: mixing sodium fluoride, potassium fluoride and lithium fluoride to obtain the electrodeposition electrolyte.
In the technical scheme, the preparation of gadolinium-doped cerium oxide powder and the electrodeposition electrolyte also comprises the steps of mixing sodium fluoride, potassium fluoride and lithium fluoride to obtain the electrodeposition electrolyte. The cell sample can be electrodeposited by mixing an electrodeposition electrolyte with gadolinium-doped cerium oxide powder.
In the technical scheme, the battery sample comprises an electrolyte layer and an anode layer, wherein the anode layer, the electrolyte layer and the compact isolating layer are sequentially laminated.
In the technical scheme, the battery sample comprises an electrolyte layer and an anode layer, wherein the anode layer, the electrolyte layer and the compact isolating layer are sequentially laminated, so that the reaction of the electrolyte and a cathode of the fuel cell can be blocked.
In the above technical solution, the anode layer includes one of the following: yttria-stabilized zirconia, scandia-stabilized zirconia, ceria-stabilized zirconia.
In the technical scheme, common materials of the anode layer are yttria-stabilized zirconia, scandia-stabilized zirconia and ceria-stabilized zirconia. Thus, the anode layer comprises one of the following: yttria-stabilized zirconia, scandia-stabilized zirconia, ceria-stabilized zirconia.
In the above technical solution, the electrolyte layer includes one of the following: yttria-stabilized zirconia, scandia-stabilized zirconia, ceria-stabilized zirconia.
In the technical scheme, common materials of the electrolyte layer are yttria-stabilized zirconia, scandia-stabilized zirconia and ceria-stabilized zirconia. Thus, the electrolyte layer comprises one of the following: yttria-stabilized zirconia, scandia-stabilized zirconia, ceria-stabilized zirconia.
In the technical scheme, the mass ratio of gadolinium-doped cerium oxide powder to the electrodeposition electrolyte is 1:100 to 3: between 100.
In the technical scheme, the sodium chloride accounts for 10-60% of the molten salt.
In the technical scheme, the potassium chloride accounts for 11-67% of the molten salt.
In the technical scheme, the lithium fluoride accounts for 12.5-72% of the molten salt.
In the technical scheme, the gadolinium nitrate accounts for 10-20% of the powder.
In the technical scheme, the cerium oxide accounts for 80-90% of the powder.
In the technical scheme, the percentage of sodium fluoride in the electrodeposition electrolyte is 8% -60%.
In the technical scheme, the potassium fluoride accounts for 8-60% of the electrodeposition electrolyte.
In the technical scheme, the lithium fluoride accounts for 14-80% of the electrodeposition electrolyte.
In order to achieve the second object of the present application, a technical solution of the second aspect of the present application provides a dense isolation layer, which is prepared by a preparation method of a dense isolation layer according to any one of the first aspect of the present application, so that the method has the technical effects of any one of the first aspect of the present application, and is not described herein again.
To achieve the third object of the present application, the technical solution of the third aspect of the present application provides a solid oxide fuel cell, which includes the dense separator according to any one of the second aspect of the present application, so that it has all the advantages of the dense separator according to any one of the second aspect of the present application, which are not described herein.
In the technical scheme, the solid oxide fuel cell comprises an electrolyte layer, an anode layer and a cathode layer, and the compact isolation layer is positioned between the electrolyte layer and the cathode layer.
In the technical scheme, the cathode layer comprises strontium lanthanum cobalt ferrite.
Additional aspects and advantages of the application will be set forth in part in the description which follows, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow chart of the steps of a method for preparing a dense isolation layer according to an embodiment of the present application.
FIG. 2 is a schematic flow chart showing the steps of a method for preparing a dense isolation layer according to an embodiment of the present application.
FIG. 3 is a schematic flow chart showing the steps of a method for preparing a dense isolation layer according to an embodiment of the present application.
FIG. 4 is a schematic flow chart showing the steps of a method for preparing a dense isolation layer according to an embodiment of the present application.
FIG. 5 is a schematic flow chart of the steps of a method for preparing a dense isolation layer according to an embodiment of the present application.
Fig. 6 is a schematic block diagram of a solid oxide fuel cell according to an embodiment of the present application.
Fig. 7 is a schematic diagram illustrating the working principle of a method for preparing a dense isolation layer according to an embodiment of the present application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will be more clearly understood, a more particular description of the application will be rendered by reference to the appended drawings and appended detailed description. It should be noted that, without conflict, the embodiments of the present application and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, however, the present application may be practiced in other ways than those described herein, and therefore the scope of the present application is not limited to the specific embodiments disclosed below.
Methods and systems for preparing a dense isolation layer, and readable storage media according to some embodiments of the present application are described below with reference to fig. 1 to 7.
As shown in fig. 1, an embodiment of the first aspect of the present application provides a method for preparing a dense isolation layer, which includes the following steps:
step S102: preparing gadolinium-doped cerium oxide powder;
step S104: preparing an electrodeposition electrolyte;
step S104: mixing gadolinium-doped cerium oxide powder with an electrodeposition electrolyte;
step S106: and (3) placing the battery sample into the mixed electrolyte for electrodeposition to obtain a compact isolation layer.
According to the preparation method of the dense isolating layer, the gadolinium-doped cerium oxide isolating layer is prepared through fused salt electrochemical deposition, the dense isolating layer can be formed in fused salt without sintering, the process is simple, the compactness is good, the reaction of electrolyte and a cathode of a fuel cell can be blocked, and the performance of the solid oxide fuel cell is improved.
Among them, gadolinium doped ceria is a ceramic electrolyte for Solid Oxide Fuel Cells (SOFCs). It has a cubic structure and a density of about 7.2g/cm in oxidized form 3 . It is a type of dopingOne of the electrolytes of ceria has a higher ionic conductivity and lower operating temperature than the yttria-stabilized zirconia materials most commonly used in SOFCs.
Specifically, a solid oxide fuel cell refers to a fuel cell that uses a solid oxide as an electrolyte and operates at high temperatures. Solid ceramic electrolytes such as zirconia stabilized with yttria are commonly used. The working temperature is 800-1000 ℃. In such fuel cells, the electromotive force is derived from different partial pressures of oxygen on both sides of the cell. The single battery consists of a positive electrode and a negative electrode (the negative electrode is a fuel electrode and the positive electrode is an oxidant electrode) and electrolyte. The main functions of the anode and the cathode are to conduct electrons and provide diffusion channels for reaction gases and product gases. The solid electrolyte separates the gases at two sides, and due to the difference of the partial pressures of oxygen at two sides, a chemical level gradient of oxygen is generated, under the action of the chemical level gradient, oxygen ions which obtain electrons at the cathode move to the anode through the solid electrolyte, and electrons are released at the anode, so that voltage is formed at two poles.
As shown in fig. 2, according to a preparation method of a dense isolation layer according to an embodiment of the present application, a battery sample is put into a mixed electrolyte to be electrodeposited, so as to obtain the dense isolation layer, which specifically includes the following steps:
step S202: placing a battery sample and a graphite plate into the mixed electrolyte, connecting the battery sample with an anode of a power supply, and connecting the graphite plate with a cathode of the power supply;
step S204: the cell sample was subjected to a current density of 0.1A/dm at 800℃to 950 ℃ 2 -1A/dm 2 And depositing for 5-30 min to form a compact isolation layer on the surface of the electrolyte layer of the battery sample.
In this example, gadolinium doped ceria in the mixed electrolyte was able to adsorb to the electrolyte layer surface of the cell sample by electrodeposition, thereby forming a dense separator layer.
Wherein, electrodeposition refers to the process of electrochemical deposition of metal or alloy from the aqueous solution, nonaqueous solution or molten salt of the metal or alloy, and the basis of the processes of metal electrowinning, electrorefining, electroplating and electroforming. The difficulty and morphology of electrodeposition of metals and the nature of the deposit are dependent on the electrolyte composition, pH, temperature, current density, and other factors.
As shown in fig. 3, according to a preparation method of a dense isolation layer according to an embodiment of the present application, gadolinium doped cerium oxide powder is prepared, which specifically includes the following steps:
step S302: mixing molten salt composed of sodium chloride, potassium chloride and lithium fluoride with powder composed of gadolinium nitrate and cerium oxide, placing the mixture in a closed tank body, sintering the mixture at 800-950 ℃, and preserving the temperature for 4-20 hours to obtain initial gadolinium-doped cerium oxide powder;
step S304: cleaning and drying the initial gadolinium-doped cerium oxide powder to obtain gadolinium-doped cerium oxide powder;
wherein, the mass ratio of the molten salt to the powder is 100:5 to 100: 60.
In this example, gadolinium nitrate is a white crystal with a density of 2.406g/cm 3 Melting point 91 deg.c, is soluble in water and alcohol and is deliquescent in humid air. Cerium oxide is an inorganic oxide with the molecular formula Ce 2 O 3 . As a white solid, hexagonal crystalline form. Belongs to ionic compounds, is difficult to dissolve in water, is easy to dissolve in strong acid, has high melting point, is obtained by reduction of cerium oxide, and is a good refractory material. Wherein, the molten salt component: powder = 100: 5-60.
As shown in fig. 4, according to a method for preparing a dense isolation layer according to an embodiment of the present application, an electrodeposition electrolyte is prepared, which specifically includes the following steps:
step S402: mixing sodium fluoride, potassium fluoride and lithium fluoride to obtain the electrodeposition electrolyte.
The cell sample can be electrodeposited by mixing an electrodeposition electrolyte with gadolinium-doped cerium oxide powder.
In the above-described embodiment, the battery sample includes the electrolyte layer and the anode layer, the electrolyte layer, and the dense separator layer are laminated in this order.
Further, common materials for the anode layer are yttria-stabilized zirconia, scandia-stabilized zirconia, and ceria-stabilized zirconia. Common materials for the electrolyte layer are yttria-stabilized zirconia, scandia-stabilized zirconia, and ceria-stabilized zirconia. A common material for the cathode layer is a perovskite ceramic material. The perovskite ceramic material may be lanthanum strontium cobalt iron.
In the above examples, the mass ratio of gadolinium doped cerium oxide powder to the electrodepositing electrolyte was 1:100 to 3: between 100.
In the above examples, sodium chloride is present in the molten salt in a percentage of 10% to 60%.
In some embodiments, the percentage of potassium chloride in the molten salt is 11% -67%.
In some embodiments, the percentage of lithium fluoride in the molten salt is 12.5% -72%.
In some embodiments, gadolinium nitrate comprises 10% -20% of the powder.
In some embodiments, the ceria comprises 80% -90% of the powder.
In some embodiments, the percentage of sodium fluoride in the electrodeposition electrolyte is 8% -60%.
In some embodiments, the percentage of potassium fluoride in the electrodeposition electrolyte is 8% -60%.
In some embodiments, the percentage of lithium fluoride in the electrodeposited electrolyte is 14% to 80%.
It can be understood that in the molten salt, the ratio of sodium chloride, potassium chloride and lithium fluoride is 1-3: 1-4: 1-5. The proportion of gadolinium nitrate and cerium oxide in the powder is 1-2: 8-9. The ratio of sodium fluoride, potassium fluoride and lithium fluoride in the electrodeposition electrolyte is 1-3: 1-3: 1-8.
An embodiment of the second aspect of the present application provides a dense isolation layer 10, which is prepared by using the method for preparing a dense isolation layer according to any one of the embodiments of the first aspect, so that the method has the technical effects of any one of the embodiments of the first aspect, and is not described herein again.
As shown in fig. 6, the embodiment of the third aspect of the present application provides a solid oxide fuel cell 20, which includes the dense separator 10 according to any of the above second aspects, and thus has all the advantages of the dense separator 10 according to any of the second aspects of the present application, and is not described herein.
In the above embodiment, the solid oxide fuel cell 20 includes the electrolyte layer 210 and the anode layer 220, the cathode layer 230, and the dense separator layer 10 is located between the electrolyte layer 210 and the cathode layer 230.
Wherein the cathode layer 230 comprises lanthanum strontium cobalt ferrite.
As shown in fig. 5 and fig. 7, a method for preparing a dense isolation layer according to an embodiment of the present application includes:
step S502: preparing GDC powder A and electrodeposited electrolyte B;
step S504: GDC powder A: electrolyte b=1 to 3:100, (mass) mixing, placing in a container, placing a sample in the container and linking with the anode of a power supply, the other end of the power supply being connected with a graphite plate, and placing in the container.
Wherein, electrodeposition process sets up: current density 0.1A/dm 2 ~1A/dm 2 Setting the temperature at 800-950 ℃ and depositing for 5-30 min.
GDC is gadolinium-doped cerium oxide, and GDC powder A is prepared by a molten salt method, and the preparation process comprises the following steps: a. NaCl: KCl: lif=1 to 3: 1-4: 1-5 parts of molten salt; b. molten salt composition and Gd (NO) 3 ) 3 :Ce 2 O 3 =1 to 10: 0.1-10 (molar ratio) of powder, and a fused salt component: powder = 100: 5-60 parts of the water tank, which are arranged in a closed tank body; c. sintering process, namely, preserving heat for 4-20 hours at 750-950 ℃; d. and (5) cleaning and drying to finish the preparation of the GDC powder.
The component B of the electrodeposition electrolyte is NaF: KF: lif=1 to 3: 1-3: 1-8 parts.
Wherein NaCl is sodium chloride, KCl is potassium chloride, liF is lithium fluoride, gd (NO) 3 ) 3 Gadolinium nitrate, ce 2 O 3 Is cerium oxide, naF is sodium fluoride, KF is potassium fluoride.
Example 1:
a method of preparing a dense isolation layer comprising:
step S1: the GDC powder A component is Gd (N)O 3 ) 3 :Ce 2 O 3 =10: 0.5 (molar ratio) composition;
step S2: the component B of the electrodeposition electrolyte is NaF: KF: lif=1: 1:1, the composition is as follows;
step S3: GDC powder A: electrolyte b=1: 100, (mass) mixing, placing in a container, placing a sample in the container and linking with the anode of a power supply, the other end of the power supply being connected with a graphite plate, and placing in the container. And (3) setting an electrodeposition process: current density 0.1A/dm 2 Setting the temperature at 800 ℃ and depositing for 5min.
The thickness of the compact isolation layer is 1-2 microns as measured by an electrolyte thickness method, and the component is (Ce 0.9 Gd 0.1 )O 1.95 。
Example 2:
a method of preparing a dense isolation layer comprising:
step S1: the GDC powder A component is Gd (NO) 3 ) 3 :Ce 2 O 3 =8: 1 (molar ratio);
step S2: the component B of the electrodeposition electrolyte is NaF: KF: lif=3: 3:8, the composition is formed;
step S3: GDC powder A: electrolyte b=2: 100, (mass) mixing, placing in a container, placing a sample in the container and linking with the anode of a power supply, the other end of the power supply being connected with a graphite plate, and placing in the container. And (3) setting an electrodeposition process: current density 1A/dm 2 Setting the temperature to 950 ℃ and depositing for 30min.
The thickness of the compact isolation layer is 1-2 microns as measured by a thickness test method, and the component is (Ce 0.80 Gd 0.20 )O 1.90 。
Example 3:
a method of preparing a dense isolation layer comprising:
step S1: the GDC powder A component is Gd (NO) 3 ) 3 :Ce 2 O 3 =9: 1 (molar ratio);
step S2: the component B of the electrodeposition electrolyte is NaF: KF: lif=2: 2:5, composing;
step S3: GDC powder A: electrolyte b=3: 100 (mass) mixingAnd placing the sample in a container, placing the sample in the container and connecting the sample with an anode of a power supply, and placing the other end of the power supply in the container in connection with the graphite plate. And (3) setting an electrodeposition process: current density 0.5A/dm 2 Setting the temperature to 850 ℃ and depositing for 20min.
The thickness of the compact isolation layer is 0.5-1 micrometer, and the component is (Ce 0.80 Gd 0.20 )O 1.90 。
In summary, the beneficial effects of the embodiment of the application are as follows:
1. the GDC isolation layer prepared by fused salt electrochemical deposition is different from the GDC isolation layer prepared by the traditional screen printing and sintering method, and the GDC isolation layer is not required to be sintered, so that a compact isolation layer is formed in fused salt.
2. The performance of the solid oxide fuel cell is improved.
In the present application, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more, unless expressly defined otherwise. The terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; "coupled" may be directly coupled or indirectly coupled through intermediaries. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.
In the description of the present application, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "front", "rear", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present application and simplifying the description, and do not indicate or imply that the apparatus or module referred to must have a specific direction, be constructed and operated in a specific direction, and thus should not be construed as limiting the present application.
In the description of the present specification, the terms "one embodiment," "some embodiments," "particular embodiments," and the like, mean 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 present application. In this specification, schematic representations of the above terms do not necessarily 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.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (20)
1. A method of preparing a dense barrier layer comprising:
preparing gadolinium-doped cerium oxide powder;
preparing an electrodeposition electrolyte;
mixing the gadolinium-doped cerium oxide powder with the electrodeposition electrolyte;
and (3) placing the battery sample into the mixed electrolyte for electrodeposition to obtain a compact isolation layer.
2. The method for preparing a dense isolating layer according to claim 1, wherein said placing a battery sample into said mixed electrolyte for electrodeposition to obtain a dense isolating layer comprises:
placing a battery sample and a graphite plate into the mixed electrolyte, connecting the battery sample with an anode of a power supply, and connecting the graphite plate with a cathode of the power supply;
the battery sample is subjected to temperature of 800 ℃ to 950 ℃ and current density of 0.1A/dm 2 -1A/dm 2 And depositing for 5-30 min, and forming a compact isolation layer on the surface of the electrolyte layer of the battery sample.
3. The method for preparing a dense isolating layer according to claim 1, wherein said preparing gadolinium doped cerium oxide powder comprises:
mixing molten salt composed of sodium chloride, potassium chloride and lithium fluoride with powder composed of gadolinium nitrate and cerium oxide, placing the mixture in a closed tank body, sintering the mixture at 800-950 ℃, and preserving the temperature for 4-20 hours to obtain initial gadolinium-doped cerium oxide powder;
cleaning and drying the initial gadolinium-doped cerium oxide powder to obtain gadolinium-doped cerium oxide powder;
wherein, the mass ratio of the molten salt to the powder is 100:5 to 100: 60.
4. The method for preparing a dense isolating layer according to claim 1, wherein said preparing an electrodeposition electrolyte solution specifically comprises:
mixing sodium fluoride, potassium fluoride and lithium fluoride to obtain the electrodeposition electrolyte.
5. A process for the preparation of a dense isolating layer as claimed in claim 1, wherein,
the battery sample includes an electrolyte layer and an anode layer, the electrolyte layer, and the dense separator layer being laminated in sequence.
6. The process for producing a dense isolating layer according to claim 5, wherein,
the anode layer includes one of: yttria-stabilized zirconia, scandia-stabilized zirconia, ceria-stabilized zirconia.
7. The process for producing a dense isolating layer according to claim 5, wherein,
the electrolyte layer includes one of: yttria-stabilized zirconia, scandia-stabilized zirconia, ceria-stabilized zirconia.
8. A process for the preparation of a dense isolating layer as claimed in claim 1, wherein,
the mass ratio of the gadolinium-doped cerium oxide powder to the electrodeposition electrolyte is 1:100 to 3: between 100.
9. A process for the preparation of a dense isolating layer as claimed in claim 3, wherein,
the sodium chloride accounts for 10-60% of the molten salt.
10. A process for the preparation of a dense isolating layer as claimed in claim 3, wherein,
the potassium chloride accounts for 11% -67% of the molten salt.
11. A process for the preparation of a dense isolating layer as claimed in claim 3, wherein,
the lithium fluoride accounts for 12.5-72% of the molten salt.
12. A process for the preparation of a dense isolating layer as claimed in claim 3, wherein,
the gadolinium nitrate accounts for 10-20% of the powder.
13. A process for the preparation of a dense isolating layer as claimed in claim 3, wherein,
the cerium oxide accounts for 80-90% of the powder.
14. The process for producing a dense isolating layer according to claim 4, wherein,
the percentage of the sodium fluoride in the electrodeposition electrolyte is 8% -60%.
15. The process for producing a dense isolating layer according to claim 4, wherein,
the potassium fluoride accounts for 8-60% of the electrodeposition electrolyte.
16. The process for producing a dense isolating layer according to claim 4, wherein,
the lithium fluoride accounts for 14-80% of the electrodeposition electrolyte.
17. A dense insulation layer prepared by the process of any one of claims 1 to 16.
18. A solid oxide fuel cell comprising the dense separator of claim 17.
19. The solid oxide fuel cell of claim 18, wherein,
the solid oxide fuel cell comprises an electrolyte layer (210), an anode layer (220) and a cathode layer (230), wherein the compact isolating layer (10) is positioned between the electrolyte layer (210) and the cathode layer (230).
20. The solid oxide fuel cell of claim 19, wherein,
the cathode layer (230) comprises lanthanum strontium cobalt ferrite.
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