CN115207425A - Solid electrolyte membrane, solid oxide fuel cell and magnetron sputtering preparation method thereof - Google Patents
Solid electrolyte membrane, solid oxide fuel cell and magnetron sputtering preparation method thereof Download PDFInfo
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- CN115207425A CN115207425A CN202210860771.2A CN202210860771A CN115207425A CN 115207425 A CN115207425 A CN 115207425A CN 202210860771 A CN202210860771 A CN 202210860771A CN 115207425 A CN115207425 A CN 115207425A
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- magnetron sputtering
- electrolyte membrane
- solid electrolyte
- fuel cell
- sputtering
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- 238000001755 magnetron sputter deposition Methods 0.000 title claims abstract description 88
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 54
- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 239000000446 fuel Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000007787 solid Substances 0.000 title claims description 34
- 238000004544 sputter deposition Methods 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims description 59
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 229910052684 Cerium Inorganic materials 0.000 claims description 32
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 32
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052726 zirconium Inorganic materials 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- 229910052772 Samarium Inorganic materials 0.000 claims description 11
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052706 scandium Inorganic materials 0.000 claims description 10
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 8
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010406 cathode material Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 abstract description 24
- 238000005245 sintering Methods 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 description 46
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 239000007789 gas Substances 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 18
- 239000010408 film Substances 0.000 description 18
- 238000001878 scanning electron micrograph Methods 0.000 description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000000919 ceramic Substances 0.000 description 10
- 229910000636 Ce alloy Inorganic materials 0.000 description 8
- 229910000748 Gd alloy Inorganic materials 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 229910000946 Y alloy Inorganic materials 0.000 description 7
- 229910001093 Zr alloy Inorganic materials 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QBYHSJRFOXINMH-UHFFFAOYSA-N [Co].[Sr].[La] Chemical compound [Co].[Sr].[La] QBYHSJRFOXINMH-UHFFFAOYSA-N 0.000 description 1
- OYVYTMATAYLZSM-UHFFFAOYSA-N [Co].[Sr].[Sm] Chemical compound [Co].[Sr].[Sm] OYVYTMATAYLZSM-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
- YLSKCQGVRKPEEA-UHFFFAOYSA-N [Fe].[Co].[Sr].[Ba] Chemical compound [Fe].[Co].[Sr].[Ba] YLSKCQGVRKPEEA-UHFFFAOYSA-N 0.000 description 1
- XGPJPLXOIJRLJN-UHFFFAOYSA-N [Mn].[Sr].[La] Chemical compound [Mn].[Sr].[La] XGPJPLXOIJRLJN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
- H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a solid electrolyte membrane, a fuel cell and a magnetron sputtering preparation method thereof. The magnetron sputtering preparation method of the solid electrolyte membrane comprises the following steps: obtaining a battery prefabricated part; preparing a solid electrolyte membrane on the surface of the battery prefabricated part by adopting a magnetron sputtering method; the conditions of the magnetron sputtering method comprise: the sputtering power is 30W-150W, and the sputtering time is 60 min-200 min. According to the magnetron sputtering preparation method of the solid electrolyte membrane, the solid electrolyte membrane in the fuel cell is prepared by using a magnetron sputtering method, and a compact solid electrolyte membrane can be prepared by matching with proper sputtering power, so that the traditional high-temperature sintering process is avoided, and the application range is wide.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a solid electrolyte membrane, a solid oxide fuel battery and a magnetron sputtering preparation method thereof.
Background
The single cell consists of an anode, an electrolyte and a cathode, wherein the anode and the cathode are electrodes. In the fuel cell, anode gas and cathode gas are respectively introduced into an anode and a cathode, and chemical reaction occurs at the connection interface of the gas, the electrode and an electrolyte, so that electric power is generated. The fuel cell requires that electrodes at two ends of an electrolyte are porous media, and gas is dispersed and guided to the surface of the electrolyte to generate chemical reaction; the electrolyte is required to be in a compact structure, the cathode and the anode are separated, oxygen ions can be transmitted, electrons and molecules cannot be transmitted, meanwhile, due to the fact that gas molecules are arranged on two sides of the electrolyte, a certain air pressure exists, if the electrolyte is not compact enough, anode hydrogen and cathode oxygen can be mixed, and potential safety hazards can be generated when the working temperature is high.
Therefore, the electrolyte compactness is very important for the electrical performance of the fuel cell. In order to realize the compactness of the electrolyte, the traditional sintering process needs to adopt a temperature of over 1200 ℃ for high-temperature sintering, otherwise, the electrolyte with good compactness is difficult to prepare, and the crosstalk of cathode and anode gases cannot be blocked to influence the electrolyte performance. However, some metal-supported solid oxide fuel cells cannot withstand high temperatures above 1100 ℃, and thus the preparation of a dense electrolyte layer is a difficult problem in the fabrication of fuel cells.
Disclosure of Invention
Based on the technical scheme, the invention provides a solid electrolyte membrane, a solid oxide fuel cell and a magnetron sputtering preparation method thereof. The magnetron sputtering preparation method of the solid electrolyte membrane can ensure that the prepared solid electrolyte membrane has better compactness, does not need high-temperature sintering and has wide application range.
In a first aspect of the present invention, a magnetron sputtering method for producing a solid electrolyte membrane is provided, including the steps of:
obtaining a battery prefabricated part;
preparing a solid electrolyte membrane on the surface of the battery prefabricated part by adopting a magnetron sputtering method;
the conditions of the magnetron sputtering method comprise: the sputtering power is 30W-150W, and the sputtering time is 60 min-200 min.
In one embodiment, the material of the solid electrolyte membrane is selected from one or more of a zirconium-based material and a cerium-based material.
In one of the embodiments, the zirconium based material is selected from zirconium based oxides and/or metal element doped zirconium based oxides;
the cerium-based material is selected from cerium-based oxide and/or metal element doped cerium-based oxide.
In one embodiment, the metal element is selected from one or more of yttrium, scandium, gadolinium and samarium.
In one embodiment, the magnetron sputtering method further includes: the working pressure is 0.5Pa to 1.5Pa, and the temperature is between room temperature and 800 ℃.
In a second aspect of the present invention, a solid electrolyte membrane prepared by the magnetron sputtering preparation method of a solid electrolyte membrane according to the first aspect is provided.
In a third aspect of the present invention, a magnetron sputtering preparation method for a solid oxide fuel cell is provided, which includes the following steps:
co-sputtering the anode material and the porous medium material by adopting a magnetron sputtering method to form a porous anode layer on the surface of the substrate;
preparing a solid electrolyte membrane on the surface of the porous anode layer according to the magnetron sputtering preparation method of the first aspect;
co-sputtering the cathode material and the porous medium material by adopting a magnetron sputtering method to form a porous cathode layer on the surface of the solid electrolyte membrane.
In one embodiment, the porous media material is selected from one or more of zirconium-based materials and cerium-based materials.
In one of the embodiments, the zirconium based material is selected from zirconium based oxides and/or metal element doped zirconium based oxides;
the cerium-based material is selected from cerium-based oxide and/or metal element doped cerium-based oxide.
In one embodiment, the metal element is selected from one or more of yttrium, scandium, gadolinium and samarium.
In one embodiment, the sputtering power ratio of the anode material or the cathode material to the porous medium material is (1-10): 1.
In one embodiment, the conditions of the magnetron sputtering method include: the sputtering power of the anode material or the cathode material is 100W-600W, the sputtering power of the porous medium material is 150W-500W, the working pressure is 0.5 Pa-1.5 Pa, the time is 5 min-200 min, and the temperature is room temperature-800 ℃.
In a fourth aspect of the invention, the solid oxide fuel cell is prepared by the magnetron sputtering preparation method of the solid oxide fuel cell in the third aspect.
According to the magnetron sputtering preparation method of the solid electrolyte membrane, the solid electrolyte membrane in the solid oxide fuel cell is prepared by using a magnetron sputtering method, and a compact solid electrolyte membrane can be prepared by matching with proper sputtering power, so that the traditional high-temperature sintering process is avoided, and the application range is wide.
Drawings
FIG. 1 is a scanning electron micrograph of a porous cathode layer prepared according to example 1 of the present invention;
FIG. 2 is a second SEM image of a porous cathode layer prepared in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of an electrolyte layer prepared according to example 1 of the present invention;
FIG. 4 is a second SEM image of the electrolyte layer prepared in example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of a porous cathode layer prepared according to example 2 of the present invention;
fig. 6 is a second scanning electron micrograph of the porous cathode layer prepared in example 2 of the present invention;
FIG. 7 is a scanning electron micrograph of an electrolyte layer prepared according to example 2 of the present invention;
FIG. 8 is a second SEM image of the electrolyte layer prepared in example 2 of the present invention;
FIG. 9 is a scanning electron micrograph of a porous cathode layer prepared according to example 3 of the present invention;
FIG. 10 is a second SEM image of a porous cathode layer prepared in example 3 of the present invention;
FIG. 11 is a scanning electron micrograph of an electrolyte layer prepared according to example 3 of the present invention;
FIG. 12 is a second SEM image of the electrolyte layer prepared in example 3 of the present invention;
FIG. 13 is a scanning electron micrograph of a porous cathode layer prepared according to example 4 of the present invention;
FIG. 14 is a second SEM image of a porous cathode layer prepared in example 4 of the present invention;
FIG. 15 is a scanning electron micrograph of an electrolyte layer prepared according to example 4 of the present invention;
FIG. 16 is a second SEM image of the electrolyte layer prepared in example 4 of the present invention;
fig. 17 is a scanning electron micrograph of an electrolyte layer prepared according to comparative example 1 of the present invention.
Detailed Description
The solid electrolyte membrane, the solid oxide fuel cell and the magnetron sputtering method for manufacturing the same according to the present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or", "and/or" includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.
As used herein, "one or more" refers to any one, any two, or any two or more of the listed items.
In the present invention, "first aspect", "second aspect", "third aspect", "fourth aspect" and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity indicating the technical feature indicated. Also, "first," "second," "third," "fourth," etc. are used for non-exhaustive enumeration of description purposes only and should not be construed as a closed limitation to the number.
In the present invention, the technical features described in the open type include a closed technical solution including the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system to which the component is added.
The temperature parameter in the present invention is not particularly limited, and is allowed to be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The room temperature in the present invention is generally 4 ℃ to 30 ℃, preferably 20. + -. 5 ℃.
The invention provides a magnetron sputtering preparation method of a solid electrolyte membrane, which comprises the following steps:
obtaining a battery prefabricated part;
preparing a solid electrolyte membrane on the surface of the battery prefabricated part by adopting a magnetron sputtering method;
the conditions of the magnetron sputtering method comprise: the sputtering power is 30W-150W, and the sputtering time is 60 min-200 min.
It is to be understood that the "preform" as described above refers to an intermediate obtained by a process prior to the production of the solid electrolyte membrane in a conventional battery production flow, and may include, for example, a substrate and an anode layer stacked in sequence, or a substrate and a cathode layer stacked in sequence, or a substrate, an anode layer, and a barrier layer stacked in sequence, or a substrate, a cathode layer, and a barrier layer stacked in sequence.
It is understood that the material used for preparing the solid electrolyte membrane is the material of the solid electrolyte membrane.
Specifically, sputtering power includes, but is not limited to: 30W, 40W, 50W, 60W, 70W, 80W, 90W, 100W, 110W, 120W, 130W, 140W and 150W.
Specifically, the magnetron sputtering method includes, but is not limited to: 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min, 180min, 190min, 200min.
In some specific examples, the porous media material is selected from one or more of a zirconium-based material and a cerium-based material. Wherein the zirconium-based material may be a zirconium-based compound, a zirconium-based oxide, zirconia, a metal element-doped zirconia, or the like. The cerium-based material may be a cerium-based compound, a cerium-based oxide, cerium oxide, metal element-doped cerium oxide, or the like.
In some specific examples thereof, the zirconium based material is selected from zirconium based oxides and/or metal element doped zirconium based oxides. Further, the metal element is selected from one or more of yttrium, scandium, gadolinium and samarium. Still further, the zirconium based material is yttrium doped zirconia YSZ (Y/Zr) and/or samarium doped zirconia SSZ (Sm/Zr).
In some specific examples thereof, the cerium-based material is selected from cerium-based oxides and/or metal element-doped cerium-based oxides. Further, the metal element is selected from one or more of yttrium, scandium, gadolinium and samarium. Still further, the cerium-based material is gadolinium doped ceria GDC (Gd/Ce) and/or scandium doped ceria SDC (Sc/Ce).
In some specific examples, the magnetron sputtering method further includes: the working pressure is more than or equal to 0.3Pa. Further, the working pressure of the magnetron sputtering method is 0.5 Pa-1.5 Pa. Specifically, the working pressure of the magnetron sputtering method includes but is not limited to: 0.5Pa, 0.6Pa, 0.7Pa, 0.8Pa, 0.9Pa, 1Pa, 1.1Pa, and 1.2Pa.
In some specific examples, the magnetron sputtering method further includes: the temperature is between room temperature and 800 ℃. Specifically, the temperature of the magnetron sputtering method includes, but is not limited to: at room temperature, 50 deg.C, 80 deg.C, 100 deg.C, 150 deg.C, 200 deg.C, 250 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C.
In some specific examples, the magnetron sputtering method further includes: the working pressure is 0.5Pa to 1.5Pa, and the temperature is between room temperature and 800 ℃.
In some specific examples, argon and oxygen are introduced during the magnetron sputtering method, and the volume ratio of the argon to the oxygen is 10 (1-5). Specifically, the volume ratio of argon to oxygen includes but is not limited to: 10.
In some specific examples, before introducing the argon and the oxygen, the vacuum degree is more than or equal to 1X 10 -6 And Pa. Further, the degree of vacuum was 1X 10 -6 Pa～1×10 -3 Pa. Specifically, vacuum levels include, but are not limited to: 1 x 10 -3 Pa、0.5×10 -3 Pa、1×10 -4 Pa、0.5×10 -4 Pa、1×10 -5 Pa、0.5×10 -5 Pa、1×10 -6 Pa. As will be appreciated, vacuum level refers to background vacuum.
In some specific examples, the pressure is maintained at the working pressure after the introduction of argon and oxygen.
It is understood that the sputtering power output mode of the magnetron sputtering method can be one or more of a direct current power supply, a radio frequency power supply, an intermediate frequency power supply and a pulse power supply. The pulse power supply can improve the sputtering power and shorten the sputtering time compared with a direct current power supply.
The invention also provides the solid electrolyte membrane prepared by the magnetron sputtering preparation method of the solid electrolyte membrane.
The invention also provides a magnetron sputtering preparation method of the solid oxide fuel cell, which comprises the following steps:
co-sputtering the anode material and the porous medium material by adopting a magnetron sputtering method to form a porous anode layer on the surface of the substrate;
preparing a solid electrolyte membrane on the surface of the porous anode layer according to the magnetron sputtering preparation method;
and co-sputtering the cathode material and the porous medium material by adopting a magnetron sputtering method to form a porous cathode layer on the surface of the solid electrolyte membrane.
The solid oxide fuel cell is a thin film cell, a thin film is deposited on the surface of a substrate, and the influence of dust, impurities and the like in the air is easily caused in the production process of the traditional sintering process, so that the uniformity of the inside of the cell thin film is influenced, the deformation of high temperature expansion caused by heat, cold contraction caused by cold and the like is difficultly resisted, the cell is easy to crack at the impurity position, and the good performance is difficultly maintained in cold and hot circulation. Meanwhile, the thickness of the electrode or electrolyte layer is more than 1 μm, the resistance is large, and the energy density of the battery is influenced and generally low. In addition, the traditional preparation process of the whole cell of the solid oxide fuel cell has more steps, the whole cell needs to be placed into a sintering furnace for sintering after deposition of processes such as coating, tape casting, screen printing and the like, all films are generally difficult to obtain at one time, the processes need to be completed step by step, the process is complex, large-scale production is difficult to carry out, the films obtained by the sintering process have larger deformation, and the films with large area and good uniformity are difficult to obtain.
The process of coating by magnetron sputtering is a process of bombarding the surface of a solid by particles (ions, atoms and molecules) with certain capacity under a vacuum state to make the atoms and molecules on the surface of the solid obtain energy to escape from the surface of the solid. According to the invention, researches show that the film obtained by the magnetron sputtering method can form a porous film or a compact film according to different materials and conditions. Based on the above, the magnetron sputtering preparation method of the fuel cell provided by the invention utilizes a magnetron sputtering method to co-sputter the electrode material and the porous medium material to form the porous electrode, and simultaneously utilizes the magnetron sputtering method to sputter the material of the solid electrolyte membrane to form a compact solid electrolyte membrane. The compact solid electrolyte membrane can transmit ions and can not transmit electrons and molecules; the porous electrodes (cathode, anode) transmit gas molecules to three-phase interfaces (electrolyte, electrode, gas three-phase) on the surface of the solid electrolyte membrane, the gas molecules electrochemically react at the three-phase interfaces, electrons are lost or obtained, the electrons pass through an external circuit to form current, and therefore electricity is generated, and ions pass through the inside of the solid electrolyte membrane.
Therefore, the magnetron sputtering preparation method of the fuel cell has the following advantages:
(1) Aiming at the problem that the film prepared by the traditional sintering process is easily influenced by dust, impurities and the like, so that the battery is easily cracked in a cold and hot cycle, the magnetron sputtering preparation method of the fuel battery is to prepare the film in a vacuum chamber, has no influence of impurities and the like, and is easy to form a high-quality film.
(2) Aiming at the problems that the thickness of a film is basically more than 1 mu m in the traditional sintering process, the resistance is large, and the energy density of a battery is influenced. The magnetron sputtering preparation method of the fuel cell can prepare the film with the minimum thickness of 1nm, the thickness of the film is reduced, the resistance is reduced, and the energy density of the cell is improved.
(3) Aiming at the traditional sintering process, the compactness of the film is ensured by high-temperature sintering, and the metal support battery cannot withstand the high temperature of over 1100 ℃. The film stacking particles obtained by the magnetron sputtering preparation method of the fuel cell are nm-grade, and a compact film can be obtained without high temperature, so that the performance of the cell is improved.
(4) Aiming at the problems that the traditional process is complex, large-scale production is difficult to carry out, the sintering process has large deformation, and a large-area film is difficult to obtain. The film is thinner and has small deformation by using the magnetron sputtering process, a large-area film battery is easy to obtain, the full battery can be produced by using the magnetron sputtering single process, the process is simple, and the large-scale production is easy to carry out.
Further, it is understood that, between the porous anode layer (porous cathode layer) and the solid electrolyte membrane, a separation layer may be sputtered by magnetron sputtering to block electrons from passing through, or to block harmful elements from chemically side-reacting with other functional components. The isolation layer has slightly different functions according to different positions, and the blocked harmful elements are different.
In some specific examples, the porous media material is selected from one or more of a zirconium-based material and a cerium-based material. Wherein the zirconium-based material may be a zirconium-based compound, a zirconium-based oxide, zirconia, a metal element-doped zirconia, or the like. The cerium-based material may be a cerium-based compound, a cerium-based oxide, cerium oxide, metal element-doped cerium oxide, or the like.
In some specific examples thereof, the zirconium based material is selected from zirconium based oxides and/or metal element doped zirconium based oxides. Further, the metal element is selected from one or more of yttrium, scandium, gadolinium and samarium. Still further, the zirconium based material is yttrium doped zirconia (Y/Zr) and/or scandium doped zirconia (Sc/Zr).
In some specific examples thereof, the cerium-based material is selected from cerium-based oxides and/or metal element doped cerium-based oxides. Further, the metal element is selected from one or more of yttrium, scandium, gadolinium and samarium. Still further, the cerium-based material is gadolinium doped ceria (Gd/Ce) and/or samarium doped ceria (Sm/Ce).
In some specific examples, the electrode material is a positive electrode material or a negative electrode material, wherein the positive electrode material includes, but is not limited to: one or more of metals such as nickel, platinum and silver and metal oxides thereof; anode materials include, but are not limited to: more than two metals of lanthanum, strontium, cobalt, iron, manganese, samarium and barium and one or more of metal oxides thereof. Further, the negative electrode material is a perovskite material, and may specifically be one or more of lanthanum strontium cobalt iron (LSCF), lanthanum Strontium Cobalt (LSC), lanthanum Strontium Manganese (LSM), samarium Strontium Cobalt (SSC) and barium strontium cobalt iron (BSCF).
In some specific examples, the ratio of the sputtering power of the electrode material to the sputtering power of the porous medium material is (1-10): 1. Correspondingly, in the porous electrode layer formed by co-sputtering, the mass ratio of the electrode material to the porous medium material is (1-10): 1. Specifically, the sputtering power ratio of the electrode material to the porous dielectric material includes but is not limited to: 1, 1.5.
It is to be understood that the substrate is not particularly limited, and may be selected from those used in conventional electrode fabrication. In some specific examples, the substrate is a metal, glass, polymer, or ceramic.
In some specific examples, the sputtering power of the electrode material is more than or equal to 100W. Further, the sputtering power of the electrode material is 100W-600W. Specifically, the sputtering power of the magnetron sputtering method includes but is not limited to: 100W, 150W, 200W, 250W, 280W, 300W, 320W, 350W, 400W, 450W, 500W, 550W and 600W.
In some specific examples, the sputtering power of the porous medium material is more than or equal to 150W. Further, the sputtering power of the porous medium material is 150W-500W. Specifically, the sputtering power of the porous medium material includes but is not limited to: 150W, 180W, 200W, 220W, 250W, 300W, 350W, 400W, 450W, 500W.
It is understood that the sputtering power output mode of the magnetron sputtering method can be one or more of a direct current power supply, a radio frequency power supply, an intermediate frequency power supply and a pulse power supply. The pulse power supply can improve the sputtering power and shorten the sputtering time compared with a direct current power supply.
In some specific examples, the magnetron sputtering method further includes: the working pressure is more than or equal to 0.3Pa. Furthermore, the working pressure of the magnetron sputtering method is 0.5 Pa-1.5 Pa. Specifically, the working pressure of the magnetron sputtering method includes but is not limited to: 0.5Pa, 0.6Pa, 0.7Pa, 0.8Pa, 0.9Pa, 1Pa, 1.1Pa, and 1.2Pa.
In some specific examples, the magnetron sputtering method further includes: the time is more than or equal to 5min. Furthermore, the time of the magnetron sputtering method is 5 min-200 min. Specifically, the magnetron sputtering method includes, but is not limited to: 5min, 10min, 15min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 150min, 170min, 200min.
In some specific examples, the magnetron sputtering method further includes: the temperature is ≧ room temperature (including but not limited to room temperature). Further, the temperature of the magnetron sputtering method is between room temperature and 800 ℃. Specifically, the magnetron sputtering method includes, but is not limited to: at room temperature, 50 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 150 deg.C, 200 deg.C, 250 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 700 deg.C, 800 deg.C.
In some specific examples, the conditions of the magnetron sputtering method include: the sputtering power is 200W-600W, the vacuum degree is 1 multiplied by 10 -6 Pa～1×10 -3 Pa, time of 5-200 min, and temperature of room temperature-800 ℃.
In some specific examples, argon and oxygen are introduced during the magnetron sputtering method, and the volume ratio of the argon to the oxygen is 10 (1-5). Specifically, the volume ratio of argon to oxygen includes but is not limited to: 10.
In some specific examples, before introducing the argon and the oxygen, the vacuum degree is more than or equal to 1X 10 -6 And Pa. Further, the degree of vacuum was 1X 10 -6 Pa～1×10 -3 Pa. Specifically, vacuum levels include, but are not limited to: 1X 10 -3 Pa、0.5×10 -3 Pa、1×10 -4 Pa、0.5×10 -4 Pa、1×10 -5 Pa、0.5×10 -5 Pa、1×10 -6 Pa. As will be appreciated, vacuum level refers to background vacuum.
In some specific examples, the operating pressure is maintained after the argon and oxygen are introduced.
The invention also provides the solid oxide fuel cell prepared by the magnetron sputtering preparation method of the solid oxide fuel cell.
The solid oxide fuel cell includes a porous anode layer, a solid electrolyte membrane, and a porous cathode layer, which are sequentially stacked. Without limitation, a separator may be added between the porous cathode layer and the solid electrolyte membrane, and/or between the porous anode layer and the solid electrolyte membrane, such as a solid oxide fuel cell comprising a porous anode layer, a separator layer, a solid electrolyte membrane, a separator layer, and a porous cathode layer, stacked in sequence.
The following are specific examples.
Example 1
This embodiment is a method for manufacturing a solid oxide fuel cell, comprising the following steps:
(1) Installing a Ni metal target, a Gd/Ce alloy target and an LSCF ceramic target, and fixing a metal substrate on a sample table;
(2) Closing the chamber cover, vacuumizing to 1 × 10 -3 Pa；
(3) Opening an argon and oxygen gas valve, and setting the gas flow to ensure that the volume ratio of argon to oxygen is 10:1, introducing gas to reach a target working pressure of 0.5Pa;
(4) Opening the sample table to rotate, and keeping the temperature of the sample table at room temperature;
(5) Communicating a direct current power supply and a radio frequency power supply, wherein the sputtering power of a Ni metal target (direct current) and the sputtering power of a Gd/Ce alloy target (pulse) are both 400W, and the Co-sputtering of Ni and Gd/Ce is started for 20min to form a porous anode layer; then sputtering (direct current) Gd/Ce for 60min at the sputtering power of 100W to form an electrolyte layer; then co-sputtering LSCF and Gd/Ce, wherein the sputtering power of an LSCF ceramic target (radio frequency) and the sputtering power of a Gd/Ce alloy target (pulse) are both 300W, the sputtering time is 30min, and a porous cathode layer is formed;
(6) After the temperature had dropped to room temperature, the sample was taken out and designated as cell 1.
And respectively detecting the porous cathode layer and the electrolyte layer by utilizing scanning electron microscope detection, wherein the scanning electron microscope images of the porous cathode layer are shown in figures 1-2, and the scanning electron microscope images of the electrolyte layer are shown in figures 3-4.
Comparative cell 1 was made in the same manner as cell 1, except that the anode, electrolyte and cathode layers were prepared using a conventional screen printing process. The electrical performance test of cell 1 and comparative cell 1 was performed at 450 c, and the peak current density of cell 1 was increased by 52% compared to comparative cell 1.
Example 2
This embodiment is a method for manufacturing a solid oxide fuel cell, comprising the following steps:
(1) Installing a Ni metal target, a Y/Zr alloy target and an LSCF ceramic target, and fixing a ceramic substrate on a sample table;
(2) Closing the chamber cover, vacuumizing to 1 × 10 -4 Pa；
(3) Opening an argon and oxygen gas valve, and setting the gas flow to ensure that the volume ratio of argon to oxygen is 10:3, introducing gas to reach the target working pressure of 0.8Pa;
(4) Starting to heat the sample table, opening the sample table to rotate, and reaching the target heating temperature of 400 ℃;
(5) Communicating a direct current power supply and a radio frequency power supply, wherein the sputtering power of an Ni metal target (direct current) and a Y/Zr alloy target (pulse) is 500W, and co-sputtering Ni and Y/Zr for 5min to form a porous anode layer; then sputtering (direct current) Y/Zr with the sputtering power of 150W and the sputtering time of 120min to form an electrolyte layer; then co-sputtering LSCF and Y/Zr, wherein the sputtering power of an LSCF ceramic target (radio frequency) and a Y/Zr alloy target (pulse) is 400W, the sputtering time is 60min, and a porous cathode layer is formed;
(6) After the temperature has dropped to room temperature, the sample is removed and marked as cell 2.
And respectively detecting the porous cathode layer and the electrolyte layer by utilizing scanning electron microscope detection, wherein the scanning electron microscope images of the porous cathode layer are shown in figures 5-6, and the scanning electron microscope images of the electrolyte layer are shown in figures 7-8.
Comparative cell 2 was made in the same manner as cell 2, except that the anode, electrolyte and cathode layers were prepared using a conventional screen printing process. Electrical performance tests were performed on cell 2 and comparative cell 2 at 500 c, and the peak current density of cell 2 was increased by 64% compared to comparative cell 2.
Example 3
This embodiment is a method for manufacturing a solid oxide fuel cell, comprising the following steps:
(1) Installing a Ni metal target, a Y/Zr alloy target, a Gd/Ce alloy target and an LSCF ceramic target, and fixing a polymer substrate on a sample table;
(2) Closing the chamber cover, vacuumizing to 1 × 10 -5 Pa；
(3) Opening an argon and oxygen gas valve, and setting the gas flow to ensure that the volume ratio of argon to oxygen is 10:2, introducing gas to reach the target working pressure of 1Pa;
(4) Starting to heat the sample table, opening the sample table to rotate to reach the target heating temperature of 800 ℃;
(5) Communicating a pulse power supply and a radio frequency power supply, starting co-sputtering Ni and Y/Zr with the sputtering power of the Ni metal target (pulse) and the sputtering power of the Y/Zr alloy target (direct current) being 400W, and forming a porous anode layer with the co-sputtering time of 60 min; then sputtering (direct current) Y/Zr with the sputtering power of 60W for 20min to form a first electrolyte layer, and then sputtering (direct current) Gd/Ce with the sputtering power of 100W for 80min to form a second electrolyte layer; then co-sputtering LSCF and Gd/Ce, wherein the sputtering power of an LSCF ceramic target (radio frequency) and the sputtering power of a Gd/Ce alloy target (pulse) are both 300W, the sputtering time is 90min, and forming a porous cathode layer;
(6) After the temperature had dropped to room temperature, the sample was taken out and recorded as cell 3.
And respectively detecting the porous cathode layer and the electrolyte layer by utilizing scanning electron microscope detection, wherein the scanning electron microscope images of the porous cathode layer are shown in figures 9-10, and the scanning electron microscope images of the electrolyte layer are shown in figures 11-12.
A comparative cell 3 was made in the same manner as cell 3, except that the anode layer, first electrolyte layer, second electrolyte layer and cathode layer were prepared using a conventional screen printing process. The electrical performance test of cell 3 and comparative cell 3 was performed at 550 c and the peak current density of cell 3 was increased by 103% compared to comparative cell 3.
Example 4
This embodiment is a method for manufacturing a solid oxide fuel cell, comprising the following steps:
(1) Installing a Ni metal target, a Y/Zr alloy target, a Gd/Ce alloy target and an LSCF ceramic target, and fixing a glass substrate on a sample table;
(2) Closing the chamber cover, vacuumizing to 1 × 10 -6 Pa；
(3) Opening an argon and oxygen gas valve, and setting the gas flow to ensure that the volume ratio of argon to oxygen is 10:4, introducing gas to reach the target working pressure of 1.2Pa;
(4) Starting to heat the sample table, opening the sample table to rotate, and reaching the target heating temperature of 300 ℃;
(5) Communicating a direct current power supply and a radio frequency power supply, wherein the sputtering power of a Ni metal target (pulse) and the sputtering power of a Gd/Ce alloy target (pulse) are both 600W, and the Ni and the Gd/Ce alloy target start to be co-sputtered for 20min to form a porous anode layer; then sputtering (direct current) Gd/Ce with the sputtering power of 30W for 200min to form a first electrolyte layer, and then sputtering (direct current) Y/Zr with the sputtering power of 110W for 150min to form a second electrolyte layer; then co-sputtering LSCF and Y/Zr, wherein the sputtering power of an LSCF ceramic target (radio frequency) and a Y/Zr alloy target (pulse) is both 500W, the sputtering time is 30min, and a porous cathode layer is formed;
(6) After the temperature had dropped to room temperature, the sample was removed and designated as cell 4.
And respectively detecting the porous cathode layer and the electrolyte layer by utilizing scanning electron microscope detection, wherein the scanning electron microscope image of the porous cathode layer is shown in figures 13-14, and the scanning electron microscope image of the electrolyte layer is shown in figures 15-16, so that the electrode is in a porous structure, the electrolyte is in a compact structure, and the structural requirements of the functional element of the solid oxide fuel cell are met.
Comparative cell 4 was made in the same manner as cell 4 except that the anode layer, first electrolyte layer, second electrolyte layer and cathode layer were prepared using a conventional screen printing process. Cell 4 and comparative cell 4 were tested for electrical performance at 450 c and the peak current density for cell 3 was improved by 79% compared to comparative cell 3.
Comparative example 1
This comparative example is a method of manufacturing a solid oxide fuel cell, which has the same steps as example 1, and is mainly different from: during the sputtering of the electrolyte layer, the sputtering power was 200W.
The electrolyte layer of the sample is detected by using a scanning electron microscope, and as a result, as shown in fig. 17, it can be seen that the prepared solid electrolyte layer is difficult to be dense and has a radially-grown porous structure. This causes the anode gas and the cathode gas to reach the opposite side through the pores, and the electrical performance test cannot be performed.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (13)
1. The magnetron sputtering preparation method of the solid electrolyte membrane is characterized by comprising the following steps of:
obtaining a battery prefabricated part;
preparing a solid electrolyte membrane on the surface of the battery prefabricated part by adopting a magnetron sputtering method;
the conditions of the magnetron sputtering method comprise: the sputtering power is 30W-150W, and the sputtering time is 60 min-200 min.
2. The magnetron sputtering production method for a solid electrolyte membrane according to claim 1, wherein a material of the solid electrolyte membrane is selected from one or more of a zirconium-based material and a cerium-based material.
3. The magnetron sputtering production method for a solid electrolyte membrane according to claim 2, wherein the zirconium-based material is selected from a zirconium-based oxide and/or a metal element-doped zirconium-based oxide;
the cerium-based material is selected from cerium-based oxides and/or metal element doped cerium-based oxides.
4. The magnetron sputtering production method for a solid electrolyte membrane according to claim 3, wherein the metal element is one or more selected from the group consisting of yttrium, scandium, gadolinium, and samarium.
5. The magnetron sputtering production method for a solid electrolyte membrane according to any one of claims 1 to 4, characterized in that the conditions of the magnetron sputtering method further include: the working pressure is 0.5Pa to 1.5Pa, and the temperature is between room temperature and 800 ℃.
6. The solid electrolyte membrane prepared by the magnetron sputtering method for preparing a solid electrolyte membrane according to any one of claims 1 to 5.
7. A magnetron sputtering preparation method of a solid oxide fuel cell is characterized by comprising the following steps:
co-sputtering the anode material and the porous medium material by adopting a magnetron sputtering method to form a porous anode layer on the surface of the substrate;
preparing a solid electrolyte membrane on the surface of the porous anode layer according to the magnetron sputtering preparation method of any one of claims 1 to 6;
co-sputtering the cathode material and the porous medium material by adopting a magnetron sputtering method to form a porous cathode layer on the surface of the solid electrolyte membrane.
8. The magnetron sputtering method for producing a solid oxide fuel cell as claimed in claim 7, wherein the porous medium material is selected from one or more of a zirconium-based material and a cerium-based material.
9. The magnetron sputtering production method for a solid oxide fuel cell according to claim 8, wherein the zirconium-based material is selected from a zirconium-based oxide and/or a metal element-doped zirconium-based oxide;
the cerium-based material is selected from cerium-based oxide and/or metal element doped cerium-based oxide.
10. The magnetron sputtering method for producing a solid oxide fuel cell as claimed in claim 9, wherein the metal element is one or more selected from the group consisting of yttrium, scandium, gadolinium and samarium.
11. The magnetron sputtering preparation method of the solid oxide fuel cell according to claim 7, wherein the sputtering power ratio of the anode material or the cathode material to the porous medium material is (1-10): 1.
12. The magnetron sputtering production method for a solid oxide fuel cell according to any one of claims 7 to 11, wherein the conditions of the magnetron sputtering method include: the sputtering power of the anode material or the cathode material is 100W-600W, the sputtering power of the porous medium material is 150W-500W, the working pressure is 0.5 Pa-1.5 Pa, the time is 5 min-200 min, and the temperature is room temperature-800 ℃.
13. The solid oxide fuel cell prepared by the magnetron sputtering preparation method of the solid oxide fuel cell in any one of claims 7 to 12.
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Application publication date: 20221018 |