CN113488665A - Reversible solid oxide battery air electrode material, preparation method and application - Google Patents
Reversible solid oxide battery air electrode material, preparation method and application Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 48
- 239000007772 electrode material Substances 0.000 title claims abstract description 37
- 230000002441 reversible effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000004888 barrier function Effects 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 4
- 229940075613 gadolinium oxide Drugs 0.000 claims description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229910002829 PrFeO3 Inorganic materials 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract 1
- 238000000840 electrochemical analysis Methods 0.000 description 13
- 239000011575 calcium Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000001453 impedance spectrum Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- -1 oxygen ion Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052804 chromium Chemical group 0.000 description 1
- 239000011651 chromium Chemical group 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 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
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
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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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to the technical field of solid oxide batteries, and particularly relates to a reversible air electrode material of a solid oxide battery, and a preparation method and application thereof. The air electrode material of the reversible solid oxide battery is characterized in that the structural formula is Pr1‑xCaxFe1‑ yCoyO3‑δWherein x is 0.1-0.9, y is 0.2-0.8, delta is 0-1, and Pr is1‑xCaxFe1‑yCoyO3‑δIs prepared by reacting with PrFeO of perovskite structure3The A site of the matrix is doped with Ca element, and the B site is doped with Co element. The invention is realized by the reaction of PrFeO3The A site is doped with Ca element, the B site is doped with Co element, the electrode material with excellent performance is obtained, and the reversible solid oxide electricity is further improvedThe electrochemical performance and the integral structural stability of the cell enable the reversible solid oxide cell to obtain excellent performance in a fuel cell mode and an electrolytic cell mode, and show good stability in a short-term cycle test.
Description
Technical Field
The invention belongs to the technical field of solid oxide batteries, and particularly relates to a reversible air electrode material of a solid oxide battery, and a preparation method and application thereof.
Background
Solid Oxide Cells (SOCs), which are electrochemical devices capable of efficiently performing energy conversion, can be operated in a Solid Oxide Fuel Cell (SOFC) mode to convert H into H2、CH4When the chemical energy of the fuel is efficiently converted into the electric energy, the surplus electric energy can be efficiently converted into the chemical energy to be stored in a Solid Oxide Electrolysis Cell (SOEC) mode. At present, the reversible electrochemical device has important significance for sustainable development and ecological environment protection, and therefore has good development prospect.
Reversible Solid Oxide Cells (RSOC) are mainly composed of three parts, an air electrode, a fuel electrode, and an electrolyte. The air electrode is O2The reduction and precipitation sites need high porosity to ensure the transmission of gas, and more particularly, the electrodes need good electrocatalytic properties, and the two aspects mainly include that one aspect needs good electronic conductivity to ensure the transmission of electrons, and the other aspect needs good oxygen ion conductivity to ensure the transmission of oxygen ions, and the two aspects are not indispensable, so that the research on the RSOC air electrode is very important. At present, many researches on air electrodes are carried out, but the finding of a material which has simple preparation process, excellent performance and wide application has a long way to go, and continuous research and improvement are needed.
CN 112290034A discloses a solid oxide fuel cell anode material, which is perovskite strontium titanate oxide powder coated by gadolinium oxide doped cerium oxide (GDC), and the general formula of the perovskite strontium titanate oxide is A1-xB1-y- zB’yB”z O3Wherein, A-bit defectB is doped, A is selected from strontium, calcium or barium, B is titanium or chromium, B 'and B' are two of manganese, iron, cobalt, nickel, scandium, niobium and molybdenum respectively, x is more than 0 and less than or equal to 0.04, y is more than 0 and less than or equal to 0.7, z is more than 0 and less than or equal to 0.1, the general formula of the gadolinium oxide doped cerium oxide is Ce0.9Gd0.1O2-mM is more than 0 and less than or equal to 0.05. According to the battery provided by the technical scheme, the B-site element of the perovskite precipitates a nano-level transition metal alloy on the framework of the anode material, the dispersion is uniform, and the battery has good capability of catalyzing and oxidizing hydrogen, but the technical scheme only has good catalytic activity on the hydrogen, does not have oxygen reduction catalytic performance, cannot be applied to an air electrode in a reversible solid oxide battery, and has an improvement space.
In summary, the prior art still lacks an electrode material that is excellent in performance and allows reversible solid oxide cells to operate at temperatures in both fuel cell mode and electrolytic cell mode.
Disclosure of Invention
Aiming at the improvement requirement of the prior art, the invention provides a reversible solid oxide battery air electrode material prepared by mixing PrFeO3The A site is doped with Ca element, and the B site is doped with Co element, so that the electrode material with excellent performance is obtained, the electrochemical performance and the integral structural stability of the reversible solid oxide battery are further improved, the reversible solid oxide battery obtains excellent performance in a fuel battery mode and an electrolytic cell mode, and the reversible solid oxide battery also shows good stability in a short-term cycle test.
In order to achieve the above object, according to one aspect of the present invention, there is provided a reversible solid oxide cell air electrode material having a structural formula of Pr1-xCaxFe1-yCoyO3-δWherein x is 0.1-0.9, y is 0.2-0.8, and delta is 0-1.
The stable valence of the Pr element at the A position is usually 3, and after the Ca element with the valence of 2 is doped at the A position, oxygen vacancies are formed because a lower-valence element replaces a higher-valence element, so that a certain number of oxygen vacancies are generated, which is beneficial to the catalytic activity of the material.
Preferably, the Pr is1-xCaxFe1-yCoyO3-δIs prepared by reacting with PrFeO of perovskite structure3The A site of the matrix is doped with Ca element, and the B site is doped with Co element.
Preferably, x is 0.1 to 0.3, preferably x is 0.2, y is 0.2 to 0.4, preferably y is 0.2.
In order to achieve the above object, according to one aspect of the present invention, there is provided a reversible solid oxide cell air electrode material having a structural formula of Pr1-xCaxFe1-a-yCoyMoaO3-δOr Pr1-xCaxFe1-a-yCoyVaO3-δWherein x is 0.1-0.9, y is 0.2-0.8, delta is 0-1, and a is less than 0.1.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing an air electrode material, comprising the steps of:
(1) calculating required metal according to the chemical dose ratio in the structural formula, dissolving the required metal in deionized water in the form of metal ion nitrate, and adding EDTA and citric acid after complete dissolution to obtain a mixed solution;
(2) adjusting the pH value of the mixed solution to 7-8, and heating until the liquid becomes gel;
(3) and baking the obtained gel at 240-300 ℃ to obtain a precursor, and grinding and calcining the precursor to obtain the air electrode material.
Preferably, the ratio of the amounts of all the metal ions, EDTA and citric acid is (1-2): (1-2): (1.5-3), preferably, molybdenum nitrate or vanadium nitrate is also added in the step (1).
In order to achieve the above object, according to one aspect of the present invention, there is provided a reversible solid oxide battery prepared from the air electrode material.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for manufacturing a reversible solid oxide cell, comprising the steps of:
(s1) preparing a support/electrolyte layer from metallic nickel-yttria-stabilized zirconia as a fuel electrode support and yttria-stabilized zirconia (YSZ) as an electrolyte layer;
(s2) coating a barrier layer on the surface of the electrolyte layer by using cerium oxide doped gadolinium oxide (GDC) as the barrier layer, and sintering to obtain a support/electrolyte layer/barrier layer;
(s3) coating the air electrode material on the surface of the barrier layer, sintering to obtain a support body/an electrolyte layer/the barrier layer/an air electrode material layer, and finally coating current collecting layers at two ends of the support body/the electrolyte layer/the barrier layer/the air electrode material layer to obtain a current collecting layer/the support body/the electrolyte layer/the barrier layer/the air electrode material layer/the current collecting layer, so that the reversible solid oxide battery can be prepared.
(s1) obtaining a support/electrolyte layer, in particular by a tabletting-degreasing-calcining process;
(s2) a barrier layer is coated on the electrolyte by screen printing and then tightly bonded by sintering.
Preferably, the sintering temperature in the step (s3) is 1000-1300 ℃, and the sintering time is 2-4 h.
To achieve the above objects, according to one aspect of the present invention, there is provided a use of a reversible solid oxide cell in a solid oxide fuel cell or a solid oxide electrolysis cell.
The invention has the following beneficial effects:
(1) the invention is realized by the reaction of PrFeO3The A site is doped with Ca element, and the B site is doped with Co element, so that the electrode material with excellent performance is obtained, the electrochemical performance and the integral structural stability of the reversible solid oxide battery are further improved, the reversible solid oxide battery obtains excellent performance in a fuel battery mode and an electrolytic cell mode, and the reversible solid oxide battery also shows good stability in a short-term cycle test. The solid oxide fuel cell and the solid oxide electrolytic cell are mutually reversible, which means that the cell runs in a solid oxide fuel cell mode to generate electric energy, or utilizes more electric energy to convert the electric energy into chemical energy to be stored in fuel gas in a solid oxide electrolytic cell mode, and the two modes can run alternately for a long time, namely the reversible solid oxygenAn oxide fuel cell.
(2) According to the invention, the doping amount is researched, the electrode material is optimized, the cell performance is improved, and the maximum power density reaches 1.672W cm under a Solid Oxide Fuel Cell (SOFC) mode at 850 DEG C-2While in the solid oxide cell (SOEC) mode of operation, 50% H is introduced on the fuel electrode side2And 50% of H2When O is added, the current density reaches 2.45A cm under the electrolytic voltage of 1.6V-2And remarkable technical effect is achieved.
Drawings
FIG. 1 is an XRD pattern of powder PCFC prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) test chart, and the left image of FIG. 2 is the morphology of the powder of the PCFC electrode; the right figure is a cross-sectional profile of the prepared battery.
Fig. 3 is an impedance spectrum of an electrochemical test in the SOFC mode using the cell prepared in example 1.
Fig. 4 is an I-V-P curve of electrochemical test in SOFC mode using the cell prepared in example 1.
Fig. 5 is an impedance spectrum of electrochemical tests performed at a temperature of 800 c under different water contents when the battery prepared using example 1 was operated in the SOEC mode.
Fig. 6 is an I-V curve of electrochemical tests performed at a temperature of 800 c at different water contents, using the battery prepared in example 1, operating in SOEC mode.
Fig. 7 is an impedance spectrum of electrochemical tests performed at different temperatures with a selected water content of 50% using the cell prepared in example 1 operated in SOEC mode.
Fig. 8 is an I-V curve of electrochemical tests conducted at various temperatures with a selected water content of 50% using the battery prepared in example 1 operated in SOEC mode.
Fig. 9 is a polarization resistance test chart of a PCFC material to which embodiment 2 is applied, in which the right side of fig. 9 is a partially enlarged view of the left side of fig. 9.
Fig. 10 is a polarization resistance test chart of a PCFCM material to which embodiment 2 is applied, in which the right side of fig. 10 is a partially enlarged view of the left side of fig. 10.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
(1) Dissolving praseodymium nitrate, calcium nitrate, ferric nitrate and cobalt nitrate into deionized water according to the proportion of 0.05mol of total substance in the electrode material, and then adding EDTA and citric acid monohydrate (the molar ratio of metal ions, EDTA and citric acid is 1: 1: 1.5) into the solution after the praseodymium nitrate, the calcium nitrate, the ferric nitrate and the cobalt nitrate are completely dissolved to obtain mixed liquid;
(2) adding ammonia water into the liquid to adjust pH value to 8, heating and stirring at 80 deg.C for 8 hr until the liquid becomes gel.
(3) Putting the obtained gel into an oven, heating to 240 ℃, preserving heat for 8h to obtain a precursor, grinding the obtained precursor, and fully calcining at 800 ℃ to obtain the PCFC perovskite material with the structural formula of Pr0.8Ca0.2Fe0.8Co0.2O2.8。
Example 2
The difference between the present example and example 1 is that molybdenum is also added to obtain PCFCM perovskite material with structural formula Pr0.8Ca0.2Fe0.8Co0.1Mo0.1O2.8
Application example 1
A battery was prepared using the material of example 1 as an air electrode, comprising the steps of:
(s1) casting to obtain Ni-YSZ/YSZ precursor, and tabletting, degreasing and calcining to obtain the support/electrolyte layer.
(s2) in order to avoid the adverse chemical reaction between the electrolyte and the electrode, GDC is selected as a barrier layer, covered on the electrolyte by screen printing, and then sintered at high temperature to tightly bond the GDC and the electrolyte.
(s3) after the electrode of PCFC prepared in example 1 was coated on the barrier layer by screen printing, it was sintered at 1000 ℃ for 2 hours, and finally both sides of the cell were coated with a platinum paste as a current collector, completing the whole cell preparation process.
Test examples
(1) After the battery piece is installed, firstly reducing the battery piece in a reducing atmosphere, and firstly introducing H2/N2Gas, then pure H is introduced2Reducing the NiO-YSZ on one side of the fuel electrode into Ni-YSZ by using the gas, and finishing the reduction process when the Open Circuit Voltage (OCV) is stable;
(2) after reduction, the cell was first tested for performance in the SOFC mode by passing air at a flow rate of 100ml/min through the air electrode side of the cell and 3% H on the fuel electrode side2H of O2The flow rate is 40ml/min, the impedance measurement is carried out at intervals of 50 ℃ in the temperature range of 700-850 ℃, and the I-V curve determination is carried out. The maximum power density of the battery is 1.672W cm at 850 DEG C-2。
(3) After the SOFC mode test, testing the performance of the battery in the SOEC mode, keeping the atmosphere of an air electrode unchanged, controlling the content of water vapor on one side of a fuel electrode by controlling the water temperature, fixing the temperature at 800 ℃, and measuring the impedance spectrum and the I-V curve of the battery under the conditions that the water content is respectively 30%, 50% and 70%, and comparing data to find that the performance of the battery is optimal under the condition that the water content is 50%; selecting 50% of H2Changing the working temperature, testing the impedance spectrum and I-V curve of the battery at 750 deg.C, 800 deg.C and 850 deg.C, and obtaining current density of 2.45A cm at 850 deg.C and 1.6V-2The battery has excellent performance of hydrogen production by water electrolysis.
(4) And then, carrying out alternate cycle stability test on the cell in the SOFC mode and the SOEC mode, respectively operating for 30min in the SOEC mode and the SOFC mode, and after alternately operating for a plurality of cycles, enabling the cell to still stably operate.
Application example 2
Batteries were prepared using the materials of examples 1 and 2 as air electrodes, comprising the following steps:
(s1) obtaining a YSZ casting sheet precursor through casting molding, and obtaining the electrolyte support sheet through a degreasing-calcining process.
(s2) in order to avoid the adverse chemical reaction between the electrolyte and the electrodes, GDC is selected as a barrier layer, covered on both sides of the electrolyte by screen printing, and then sintered at high temperature to tightly bond the GDC and the electrolyte.
(s3) after the PCFC electrode and PCFCM electrode materials prepared in example 1 and example 2 were respectively brushed on the barrier layer by screen printing method, they were sintered at 1000 ℃ for 2h, finally both sides of the cell were coated with a layer of platinum paste as current collector, and the whole process of preparation of symmetrical cell was completed.
Test examples
(1) After the battery piece is installed, heating to 700 ℃, and starting a test process when Open Circuit Voltage (OCV) is stable;
(2) passing water-laden air (water content of 3%) at a flow rate of 50ml/min through both sides of the cell, measuring impedance at intervals of 50 ℃ within a temperature range of 600-800 ℃, recording data and comparing.
FIG. 1 is an XRD pattern of PCFC powder prepared in example 1. As is clear from fig. 1, the PCFC powder has an orthorhombic perovskite structure.
FIG. 2 is a Scanning Electron Microscope (SEM) test chart, and the left image in FIG. 2 is the morphology of the powder of the PCFC electrode; the right picture is a sectional topography picture of the prepared battery, and the morphology of the powder of the PCFC electrode and the sectional topography picture of the prepared battery are represented.
As can be seen from FIG. 2, the electrode material has a loose and porous structure, and the particles are fine and uniform; the battery has the advantages of clear structure, porous electrodes, compact electrolyte and thin barrier layer.
Fig. 3 is an impedance spectrum of an electrochemical test in the SOFC mode using the cell prepared in example 1. Fig. 4 is an I-V-P curve of electrochemical test in SOFC mode using the cell prepared in example 1.
As can be seen from fig. 3 and 4, the electrode material has excellent performance when applied in the SOFC mode, and can obtain a high power density.
Fig. 5 is an impedance spectrum of electrochemical tests performed at a temperature of 800 c under different water contents when the battery prepared using example 1 was operated in the SOEC mode.
Fig. 6 is an I-V curve of electrochemical tests performed at a temperature of 800 c at different water contents, using the battery prepared in example 1, operating in SOEC mode.
As can be seen from fig. 5 and 6, when the temperature is 800 ℃, the electrochemical test is performed by introducing 30%, 50% and 70% water content, respectively, and when the water content is increased from 30% to 50%, the impedance is significantly decreased and the performance is significantly improved, and when the water content is increased from 50% to 70%, the performance is not significantly improved, so we select the 50% water content as the test condition.
Fig. 7 is an impedance spectrum of electrochemical tests performed at different temperatures with a selected water content of 50% using the cell prepared in example 1 operated in SOEC mode.
Fig. 8 is an I-V curve of electrochemical tests conducted at various temperatures with a selected water content of 50% using the battery prepared in example 1 operated in SOEC mode.
As can be seen from fig. 7 and 8, as the temperature increases, the impedance of the battery decreases with a constant water content, and the performance increases.
Fig. 9 is a polarization resistance test chart of a PCFC material to which embodiment 2 is applied, in which the right side of fig. 9 is a partially enlarged view of the left side of fig. 9.
Fig. 10 is a polarization resistance test chart of a PCFCM material to which embodiment 2 is applied, in which the right side of fig. 10 is a partially enlarged view of the left side of fig. 10.
As can be seen from fig. 9 and 10, by impedance comparison, after the B site is doped with Mo, the polarization impedance of the electrode material is significantly reduced, so that we believe that the PCFC has excellent performance as an air electrode of a reversible solid oxide cell, and when we further dope the B site, the performance is also significantly improved. Therefore, the material has further research potential.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The air electrode material of the reversible solid oxide battery is characterized in that the structural formula is Pr1-xCaxFe1-yCoyO3-δWherein x is 0.1-0.9, y is 0.2-0.8, and delta is 0-1.
2. The air electrode material of claim 1, wherein the Pr is1-xCaxFe1-yCoyO3-δIs prepared by reacting with PrFeO of perovskite structure3The A site of the matrix is doped with Ca element, and the B site is doped with Co element.
3. The air electrode material according to claim 1 or 2, wherein x is 0.1-0.3, preferably x is 0.2 and y is 0.2-0.4, preferably y is 0.2.
4. The air electrode material of the reversible solid oxide battery is characterized in that the structural formula is Pr1-xCaxFe1-a- yCoyMoaO3-δOr Pr1-xCaxFe1-a-yCoyVaO3-δWherein x is 0.1-0.9, y is 0.2-0.8, delta is 0-1, and a is less than 0.1.
5. The method for producing an air electrode material according to any one of claims 1 to 4, characterized by comprising the steps of:
(1) calculating required metal according to the chemical dose ratio in the structural formula, dissolving the required metal in deionized water in the form of metal ion nitrate, and adding EDTA and citric acid after complete dissolution to obtain a mixed solution;
(2) adjusting the pH value of the mixed solution to 7-8, and heating until the liquid becomes gel;
(3) and baking the obtained gel at 240-300 ℃ to obtain a precursor, and grinding and calcining the precursor to obtain the air electrode material.
6. The method for producing an air electrode material according to claim 5, wherein the ratio of the amounts of all the metal ions, EDTA and citric acid is (1-2): (1-2): (1.5-3).
7. A reversible solid oxide cell made with the air electrode material of any of claims 1-4.
8. The method of manufacturing a reversible solid oxide cell according to claim 7, characterized by comprising the steps of:
(s1) preparing a support/electrolyte layer using metallic nickel-yttria-stabilized zirconia as a fuel electrode support and yttria-stabilized zirconia as an electrolyte layer;
(s2) coating a barrier layer on the surface of the electrolyte layer by using cerium oxide doped gadolinium oxide as the barrier layer, and sintering to obtain a support/electrolyte layer/barrier layer;
(s3) coating the air electrode material on the surface of the barrier layer, sintering to obtain a support body/an electrolyte layer/the barrier layer/an air electrode material layer, and finally coating current collecting layers at two ends of the support body/the electrolyte layer/the barrier layer/the air electrode material layer to obtain a current collecting layer/the support body/the electrolyte layer/the barrier layer/the air electrode material layer/the current collecting layer, so that the reversible solid oxide battery can be prepared.
9. The method of manufacturing a reversible solid oxide cell according to claim 8, characterized in that in step (s3), the sintering temperature is 1000 ℃ to 1300 ℃ and the sintering time is 2h to 4 h.
10. Use of a reversible solid oxide cell according to claim 7 in a solid oxide fuel cell or a solid oxide electrolysis cell.
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