A solid oxide fuel cell anode material and a preparation method of a battery comprising the same

Abstract

The present invention discloses a solid oxide fuel cell anode material and a preparation method of a battery comprising the material. It is prepared by a solid-phase method from compound raw materials containing Sr 2+ , compound raw materials containing Fe 3+ , and compound raw materials containing Ta 5+ . The chemical formula of the material of the present invention is SrFe 1‑x Ta x O 3‑δ (0 < x ≤ 0.2). The solid oxide fuel cell anode material of the present invention has structural stability both in air and hydrogen. At the same time, it has good compatibility with the electrolyte material La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 2.85 . The solid oxide fuel cell prepared with the present invention as the anode material has excellent electrochemical performance and a simple preparation process.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid oxide fuel cells, and relates to an anode material for a solid oxide fuel cell and a preparation method of a battery comprising the material. Background Art

[0002] While the social economy is developing rapidly, the energy required by humans is increasing. However, the problems of energy consumption and environmental pollution caused by the material materials mainly based on traditional fossil energy are becoming increasingly serious. It is reported that most of the global energy consumption is concentrated in the consumption of fossil energy such as coal and oil. Developing new energy and new energy storage technologies is urgent for solving the energy problems encountered in today's society. A solid oxide fuel cell is an energy conversion device that can directly convert chemical energy into electrical energy. Usually, it uses hydrogen or hydrocarbon fuel as the fuel gas, oxygen or air as the oxidizing gas, and water as the discharge product. As long as the products are sufficient and the battery structure is reliable, the fuel cell can supply power continuously for several years without causing environmental pollution, which is a high-quality field worthy of our continuous research and innovation.

[0003] The traditional anode material of a solid oxide fuel cell is a nickel-based anode material, which can effectively catalyze the chemical reaction of the fuel gas. However, during the catalysis, carbon deposition is likely to occur, thereby covering the active sites of the reaction between the fuel gas and the material, and also causing the anode to expand, thus damaging the internal structure and causing lattice collapse. Therefore, it is of great significance to invent a solid oxide fuel cell anode material with a stable structure and anti-carbon deposition. The material of the present invention has a stable perovskite structure in both air and hydrogen, and can resist carbon deposition to a certain extent. The solid oxide fuel cell prepared with the material of the present invention has good performance. Summary of the Invention

[0004] One of the purposes of the present invention is to provide a solid oxide fuel cell anode material with a stable structure and anti-carbon deposition.

[0005] Another purpose of the present invention is to provide a preparation method of the above-mentioned solid oxide fuel cell anode material with a stable structure and anti-carbon deposition.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows: A solid oxide fuel cell anode material with a stable structure and anti-carbon deposition, the chemical formula of the material is SrFe 0.9 Ta 0.1 O 3-δ , where δ is a value to ensure the electrical neutrality of the material.

[0007] The present invention also provides a preparation method of the above-mentioned solid oxide fuel cell anode material with a stable structure and anti-carbon deposition, comprising the following steps:

[0008] (1) Containing Sr2+ compounds containing Fe 3+ compounds containing Ta 5+ compound raw materials, weigh each raw material according to the stoichiometric ratio of the corresponding metal elements in the chemical formula SrFe 0.9 Ta 0.1 O 3-δ ;

[0009] (2) Mix the powders weighed in step (1) and put them into a mortar, then add anhydrous ethanol and grind to make them fully mixed, and then dry to form a powder;

[0010] (3) Put an appropriate amount of the mixed powder obtained in step (2) into a mold and press it into a tablet;

[0011] (4) Put the tablet pressed in step (3) into a muffle furnace and calcine it at 950 - 1050 °C for 9 - 11 hours in an air atmosphere;

[0012] (5) After grinding the calcined tablet above, add anhydrous ethanol and grind to make it fully mixed, and then dry to form a powder;

[0013] (6) Put an appropriate amount of the powder obtained in step (5) above into a mold and press it into a tablet;

[0014] (7) Put the tablet pressed in step (6) into a high-temperature furnace and calcine it at 1050 - 1150 °C for 9 - 11 hours in an air atmosphere;

[0015] (8) Repeat step (5), after obtaining the powder, put an appropriate amount into a mold and press it into a tablet;

[0016] (9) Put the tablet pressed in step (8) above into a high-temperature furnace and calcine it at 1300 - 1400 °C for 9 - 11 hours in an air atmosphere;

[0017] (10) Put the sintered tablet in step (9) above, after cooling, put it into a high-temperature tube furnace and calcine it at 800 - 900 °C for 9 - 11 hours in a 5% H2 / 95% Ar atmosphere;

[0018] (11) Grind the tablet after reduction in step (10), add anhydrous ethanol and grind, and after drying, obtain SrFe 0.9 Ta 0.1 O 3-δ solid oxide fuel cell anode electrode powder.

[0019] Preferably, in step (1), the compound containing Sr 2+ is SrCO3, the compound containing Fe 3+ is Fe2O3, and the compound raw material containing Ta 5+ is Ta2O5.

[0020] Preferably, in steps (3) and (6), tabletting is specifically carried out by placing the material in a mold with a diameter of 20 mm and pressing it into tablets under a pressure of 10 MPa.

[0021] Preferably, in step (8), tabletting is specifically carried out by placing the material in a mold with a diameter of 13 mm and pressing it into tablets under a pressure of 4 MPa.

[0022] The present invention also provides a solid oxide fuel cell prepared from a solid oxide fuel cell anode material with stable structure and anti-carbon deposition, which is characterized by including the following steps:

[0023] (1) Select the obtained SrFe 0.9 Ta 0.1 O 3-δ solid oxide fuel cell anode electrode powder, add a certain amount of binder and grind it until uniform to make the anode electrode paste;

[0024] (2) Then select an appropriate amount of SmBaCo2O 5+δ as the cathode powder, add a certain amount of binder and grind it until uniform to make the cathode electrode paste;

[0025] (3) Uniformly coat the electrode pastes prepared in steps (1) and (2) on both sides of the electrolyte sheet La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 2.85 and dry it to obtain a battery sheet;

[0026] (4) Place the dried battery sheet in a high-temperature tubular furnace and sinter it in an N2 atmosphere at 900-1000 °C for 1-3 hours to obtain a solid oxide fuel cell with SrFe 0.9 Ta 0.1 O 3-δ material as the anode material.

[0027] Preferably, in step (1), the mass ratio of the SrFe 0.9 Ta 0.1 O 3-δ anode powder material to the binder is 1:1.5; the binder is composed of terpineol and ethyl cellulose mixed in a mass ratio of 9:1.

[0028] Preferably, in step (2), the thickness of the electrolyte sheet La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 2.85 is 0.3 mm.

[0029] The present invention provides a solid oxide fuel cell anode material with stable structure and anti-carbon deposition, and a preparation method thereof. In terms of chemical composition, the chemical formula of the electrode material is SrFe 0.9 Ta 0.1 O 3-δ , which has good chemical compatibility with the electrolyte material La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 2.85 Under both air and hydrogen, it has a stable perovskite structure. SrFeO3-based perovskite materials are considered promising anode materials for intermediate-temperature SOFCs and have excellent electrocatalytic activity. However, the lattice structure of SrFeO3 is unstable. It has been found that doping at the B-site is an effective method to stabilize its lattice structure. The SrFe 0.9 Ta 0.1 O 3-δ anode material provided by the present invention replaces part of Fe with Ta at the B-site of the perovskite, significantly improving the structural stability of the electrode material and the anti-carbon deposition property of the solid oxide fuel cell prepared.

[0030] The example results show that for the solid oxide fuel cell anode material with stable structure and anti-carbon deposition provided by the present invention, through XRD characterization, no impurity peaks are generated under air and hydrogen, and it is a stable perovskite structure; for the solid oxide fuel cell prepared with the anode material provided by the present invention, the maximum output power at 850 °C in H2 atmosphere is 793 mW cm -2 , and the maximum output power at 900 °C in CH4 atmosphere is 350 mW cm -2 , showing excellent anti-carbon deposition property and good electrochemical performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 XRD pattern of SrFe 0.9 Ta 0.1 O 3-δ synthesized in air.

[0032] Figure 2 XRD pattern of SrFe 0.9 Ta 0.1 O 3-δ after reduction with 5% H2 / 95% Ar.

[0033] Figure 3 Power density diagram of the anode full cell of the material SrFe 0.9 Ta 0.1 O 3-δ in H2 atmosphere.

[0034] Figure 4For the material SrFe of the present invention 0.9 Ta 0.1 O 3-δ is the power density diagram of the anode full cell in a CH4 atmosphere. Detailed implementation manners

[0035] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific implementation steps, but the present invention is not limited to the following examples.

[0036] The present invention provides a preparation method for an anode material of a solid oxide fuel cell with stable structure and anti-carbon deposition, including the following steps:

[0037] (1) Weigh the raw materials SrCO3, Fe2O3, and Ta2O5 according to a molar ratio of 1:0.45:0.05;

[0038] (2) Mix the powders weighed in step (1) and put them into a mortar, then add anhydrous ethanol and grind them to make them fully mixed, and then dry them into powders;

[0039] (3) Appropriately put the mixed powder obtained in step (2) into a mold with a diameter of 20 mm and press it into a sheet with a pressure of 10 MPa;

[0040] (4) Put the sheet pressed in step (3) into a muffle furnace and calcine it at 1000 °C for 10 hours in an air atmosphere;

[0041] (5) After grinding the calcined sheet above, add anhydrous ethanol and grind it to make it fully mixed, and then dry it into a powder;

[0042] (6) Appropriately put the powder obtained in step (5) above into a mold with a diameter of 20 mm and press it into a sheet with a pressure of 10 MPa;

[0043] (7) Put the sheet pressed in step (6) into a high-temperature furnace and calcine it at 1100 °C for 10 hours in an air atmosphere;

[0044] (8) Repeat step (5), after obtaining the powder, take 0.3 g and put it into a mold with a diameter of 13 mm and press it into a sheet with a pressure of 4 MPa;

[0045] (9) Put the sheet pressed in step (8) above into a high-temperature furnace and calcine it at 1350 °C for 10 hours in an air atmosphere;

[0046] (10) After cooling the sheet sintered in step (9) above, put it into a high-temperature tubular furnace and calcine it at 850 °C for 10 hours in a 5% H2 / 95% Ar atmosphere;

[0047] (11) After grinding the sheet reduced in step (10), add anhydrous ethanol and grind it, and after drying, obtain SrFe0.9 Ta 0.1 O 3-δ Solid oxide fuel cell anode electrode powder.

[0048] A solid oxide fuel cell prepared from a solid oxide fuel cell anode material with stable structure and anti-carbon deposition is characterized by the following steps:

[0049] (1) Select the SrFe 0.9 Ta 0.1 O 3-δ solid oxide fuel cell anode electrode powder obtained above, add a binder (the mass ratio of the anode powder material to the binder is 1:1.5; the binder is composed of terpineol and ethyl cellulose mixed in a mass ratio of 9:1) and grind it until it is uniform to make an anode electrode slurry;

[0050] (2) Then select an appropriate amount of SmBaCo2O 5+δ as the cathode powder, add a certain amount of binder and grind it until it is uniform to make a cathode electrode slurry (the SmBaCo2O 5+δ cathode powder is formed by solid-phase method and sintered at 1150 °C for 10 hours);

[0051] (3) Coat the electrode slurries prepared in steps (1) and (2) evenly on both sides of an electrolyte sheet La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 2.85 with a thickness of 0.3 mm and dry it to obtain a cell sheet (the electrolyte sheet is sintered at 1400 °C for 10 hours by dry pressing method to form a dense LSGM electrolyte sheet);

[0052] (4) Place the dried cell sheet in a high-temperature tube furnace and sinter it at 950 °C for 2 hours in an N2 atmosphere to obtain a solid oxide fuel cell with SrFe 0.9 Ta 0.1 O 3-δ material as the anode material;

[0053] (5) Seal the single cell prepared in step (4) with silver paste at one end of a ceramic tube and fix it in a muffle furnace. Pass the fuel gas into the anode gas channel of the solid oxide fuel cell, and pass the outside air into the cathode gas channel of the solid oxide fuel cell. The chemical energy is converted into electrical energy by the gain and loss of electrons at the cathode and anode and output direct current to the outside to perform the test of electrochemical performance.

[0054] Use an X-ray diffractometer to perform a phase analysis on the SrFe 0.9 Ta 0.1 O 3-δ anode powder material prepared by the present invention and compareFigure 1 and Figure 2 indicate that the material of the present invention has a stable cubic perovskite phase both in air and hydrogen. After reduction, no impurity peaks are generated. It shows that SrFe 0.9 Ta 0.1 O 3-δ has a stable material structure.

[0055] An electrochemical workstation is used to perform electrochemical performance tests on a full cell with the material SrFe 0.9 Ta 0.1 O 3-δ of the present invention as the anode material. The power densities of the cell under H2 and CH4 are as shown in Figure 3 and Figure 4 . It can be seen from Figure 3 that the maximum output power at 850 °C in a H2 atmosphere is 793 mW cm -2 , and the maximum output power at 900 °C in a CH4 atmosphere is 350 mW cm -2 . It shows excellent anti-coking performance and good electrochemical performance.

[0056] The above are only the preferred experimental cases of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope covered by the present invention.

Claims

1. A method for preparing an anode material of a solid oxide fuel cell, characterized in that It includes the following steps: S1.1: Using a compound containing Sr 2+ and a compound containing Fe 3+ and a compound containing Ta 5+ as raw material compounds, according to Chemical formula SrFe 1-x Ta x O 3-δ Weigh each raw material according to the stoichiometric ratio of the corresponding metal elements in (0 < x ≤ 0.2); S1.2: Put the powder obtained by weighing in step S1.1 into a mortar, then add absolute ethanol and grind it to make it fully mixed, and then dry it into powder; S1.3: Put an appropriate amount of the mixed powder obtained in step S1.2 into a mold and press it into a tablet; S1.4: Put the tablet pressed in step S1.3 into a muffle furnace and calcine it at 950 - 1050 °C for 9 - 11 hours in an air atmosphere to obtain a calcined tablet; S1.5: After grinding the tablet calcined in step S1.4 above, add absolute ethanol and grind it to make it fully mixed, and then dry it into powder; S1.6: Put an appropriate amount of the powder obtained in step S1.5 above into a mold and press it into a tablet; S1.7: Put the tablet pressed in step S1.6 into a high-temperature furnace and calcine it at 1050 - 1150 °C for 9 - 11 hours in an air atmosphere; S1.8: Repeat step S1.5, after obtaining the powder, put an appropriate amount into a mold and press it into a tablet; S1.9: Put the tablet pressed in step S1.8 above into a high-temperature furnace and calcine it at 1300 - 1400 °C for 9 - 11 hours in an air atmosphere; S1.10: After cooling the tablet calcined in step S1.9 above, put it into a high-temperature tube furnace and calcine it at 800 - 900 °C for 9 - 11 hours in a 5% H2 / 95% Ar atmosphere; The specific process of pressing the tablets in steps S1.3 and S1.6 is to put them into a mold with a diameter of 20 mm and press them with a pressure of 10 MPa. The specific process of pressing the tablet in step S1.8 is to put it into a mold with a diameter of 13 mm and press it with a pressure of 4 MPa. It includes the following steps: ​ ​ S1.11 After grinding the flakes obtained by calcining in step S1.10, add anhydrous ethanol and grind, and obtain SrFe after drying 1- x Ta x O 3-δ Solid oxide fuel cell anode electrode powder.

2. The preparation method of a solid oxide fuel cell anode material according to claim 1, characterized in that Step S1.1 uses a compound SrCO3 containing Sr 2+ , a compound Fe2O3 containing Fe 3+ , and a compound Ta2O5 containing Ta 5+ as raw materials.

3. The preparation method of a solid oxide fuel cell anode material according to claim 1, characterized in that, ​ 4. A method for preparing a solid oxide fuel cell anode material according to claim 1, characterized in that, ​ 5. A method for preparing a solid oxide fuel cell, characterized in that, ​ S5.1: Select SrFe obtained by the preparation method as claimed in claim 1 1-x Ta x O 3-δ Take the anode material of the solid oxide fuel cell as electrode powder, add a certain amount of binder and grind it until it is uniform to make an anode electrode paste; S5.2: Then select an appropriate amount of SmBaCo2O 5+δ as the cathode powder, add a certain amount of binder and grind it until it is uniform to make the cathode electrode paste; S5.3: Uniformly coat the electrode slurries prepared in steps S5.1 and S5.2 on both sides of the electrolyte sheet La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 2.85 and dry them to obtain battery cells; S5.4: Place the dried solar cells in a high-temperature tube furnace and sinter them at 900 - 1000 °C for 1 - 3 hours under N2 atmosphere to obtain a solid oxide fuel cell with SrFe 1-x Ta x O 3-δ material as the anode material.

6. The preparation method according to claim 5, characterized in that, In step S5.1, SrFe 1-x Ta x O 3-δ The mass ratio of the anode powder material to the binder is 1:1.5; the binder is composed of terpineol and ethyl cellulose mixed in a mass ratio of 9:

1.

7. The preparation method according to claim 5, characterized in that, In step S5.2, the thickness of the electrolyte sheet La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 2.85 is 0.3 mm.

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