CN110336041B - Ruthenium-nickel composite electrode and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of solid oxide fuel cell electrode preparation, and particularly relates to a ruthenium-nickel composite electrode and a preparation method and application thereof. The method comprises the steps of dripping a precursor solution of ruthenium on a nickel-based electrode body, standing, drying, roasting and cooling in sequence to prepare a ruthenium oxide nickel-based composite electrode, repeating the steps until the content of ruthenium in the nickel-based electrode body is 0.5-3wt%, and finally reducing the treated ruthenium oxide nickel-based composite electrode to prepare the ruthenium-nickel composite electrode, wherein the electrode prepared by the method has good ammonia decomposition catalytic activity and electrical conductivity; in addition, the electrode has better ammonia decomposition catalytic activity, can provide more hydrogen for the battery, and the ruthenium-based catalyst has better low-temperature activity, so that the low-temperature electrochemical performance of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of SOFC electrode preparation, and particularly relates to a ruthenium-nickel composite electrode and a preparation method and application thereof.
Background
Due to the problems of environmental pollution, greenhouse effect and the like, an energy structure mainly based on the traditional carbon-based energy faces huge challenges, and hydrogen energy is considered as an alternative energy source of future fossil fuels due to the advantages of cleanness, high energy density per unit mass, wide sources and the like. With the gradual industrialization of hydrogen fuel cell technology, high-efficiency and carbon-free utilization of hydrogen energy will be realized. At present, a key difficult problem to be solved is an efficient and safe hydrogen storage technology.
Ammonia is not only an important inorganic chemical product, but it also has unique advantages as a hydrogen carrier. The ammonia is easy to liquefy, has pungent smell, is non-flammable, non-toxic at low concentration, high in hydrogen storage density, mature in production, storage and transportation technology, and free of carbon emission in the hydrogen production process, and is an efficient, clean and safe hydrogen storage carrier.
The direct ammonia Solid Oxide Fuel Cell (SOFC) can directly convert ammonia into stable electric energy, but because the anode of the traditional SOFC adopts a nickel-based material, the ammonia catalytic activity of non-noble metal nickel at low temperature is obviously reduced, so that the electrochemical performance of the direct ammonia SOFC below low temperature (600 ℃) is obviously reduced. Ruthenium has high ammonia decomposition low-temperature catalytic activity and stability, but the ammonia catalytic activity of ruthenium is closely related to a carrier, an auxiliary agent and a preparation method.
Chinese patent document CN103422116A discloses a preparation method of a porous nickel-based ruthenium oxide composite hydrogen evolution electrode, which comprises pretreating a nickel substrate, preparing a porous nickel-based precursor electrode by electrodeposition, and depositing an electrolyte of ruthenium chloride, glycine and sodium nitrate on the electrode to obtain the porous nickel-based ruthenium oxide composite electrode, but the electrode does not specifically design ammonia activation; the anode of the direct ammonia SOFC is a metal ceramic electrode mixed with nickel and a solid oxide ion conductor material, and a corresponding preparation method needs to be developed to realize stable load and high ammonia catalytic activity of ruthenium.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of poor ammonia catalytic activity, poor low-temperature electrochemical performance and the like in the direct ammonia SOFC electrode in the prior art, so that the preparation method of the ruthenium-nickel composite ammonia decomposition hydrogen production electrode is provided.
Therefore, the invention provides the following technical scheme.
The invention provides a preparation method of a ruthenium-nickel composite electrode, which comprises the following steps,
(1) dripping a precursor solution of ruthenium on a nickel-based electrode body, standing and drying;
(2) sequentially roasting and cooling the nickel-based electrode body to prepare a ruthenium oxide nickel-based composite electrode;
(3) weighing and calculating the ruthenium content in the ruthenium oxide nickel-based composite electrode, and repeating the steps (1) and (2) until the ruthenium content in the nickel-based electrode body is 0.5-3 wt%;
(4) and (4) reducing the ruthenium oxide nickel-based composite electrode treated in the step (3) to obtain the ruthenium-nickel composite electrode.
The nickel-based electrode body comprises an electrode plate and an electrolyte layer arranged on the electrode plate, wherein the electrolyte layer comprises a first material and a second material, and the first material is one of barium-based perovskite, zirconia-based rare earth metal oxide, cerium oxide-based rare earth metal oxide and lanthanum gallate-based perovskite; the second material is a nickel source;
the zirconia-based rare earth metal oxide is yttria-stabilized zirconia or scandia-stabilized zirconia;
the cerium oxide-based rare earth metal oxide is gadolinium-doped cerium oxide or strontium-doped cerium oxide;
the barium-based perovskite is zirconium yttrium doped barium cerate, zirconium yttrium ytterbium doped barium cerate or yttrium doped barium zirconate;
the lanthanum gallate-based perovskite is lanthanum gallate doped with zirconium, strontium and magnesium.
The mass ratio of the first material to the second material is 3:7-6: 4.
The precursor in the ruthenium precursor solution is at least one of ruthenium chloride, ruthenium nitrate, ruthenium acetate or ruthenium acetylacetonate;
the solvent of the precursor solution of ruthenium is water or ethanol; the mass fraction of the precursor in the precursor solution of ruthenium is 3-15%.
Further, the standing time is 0.5-1.5 h;
the drying temperature is 80-120 ℃, and the drying time is 0.4-1.2 h.
The roasting temperature is 400-500 ℃, and the roasting time is 15-30 min.
Further, before the roasting, the method also comprises the step of heating the nickel-based electrode body to 400-500 ℃ at the heating rate of 1-1.5 ℃/min.
And (3) the reduction is carried out by placing the ruthenium oxide nickel-based composite electrode treated in the step (3) in a hydrogen atmosphere, wherein the reduction temperature is 600-800 ℃, and the reduction time is 0.5-2 h.
The invention also provides a ruthenium-nickel composite electrode prepared by the preparation method.
In addition, the invention also provides an application of the ruthenium-nickel composite electrode prepared by the method or the application of the ruthenium-nickel composite electrode in a direct ammonia solid oxide fuel cell.
The technical scheme of the invention has the following advantages:
1. the preparation method of the ruthenium-nickel composite electrode comprises the steps of dripping a precursor solution of ruthenium on a nickel-based electrode body, standing, drying, roasting and cooling in sequence to prepare the ruthenium oxide nickel-based composite electrode, repeating the steps until the content of ruthenium in the nickel-based electrode body is 0.5-3wt%, and finally reducing the treated ruthenium oxide nickel-based composite electrode to prepare the ruthenium-nickel composite electrode. The electrode prepared by the method has good ammonia decomposition catalytic activity and electrical conductivity, because ruthenium is in a submicron scale, more catalytic and electrochemical active point sites can be provided, the reaction interface is improved, the ammonia decomposition catalytic activity and the electrochemical oxidation reaction rate of the electrode are improved, meanwhile, ruthenium can form a submicron particle layer on the electrode, a new electron conduction path is provided for the SOFC electrode, and the electrical conductivity of the electrode is improved; in addition, the electrode has better ammonia decomposition catalytic activity, can provide more hydrogen for the battery, and the ruthenium-based catalyst has better low-temperature activity, so that the low-temperature electrochemical performance of the battery is improved.
2. According to the preparation method of the ruthenium-nickel composite electrode, the carrier adopted by the method can be used as an ion conductor material of the electrode body, so that the three-phase interface of electrochemical reaction can be further enriched, and the electrochemical reaction is promoted to occur; the carrier can also be used as a ruthenium-loaded carrier, and has good loading stability.
3. According to the preparation method of the ruthenium-nickel composite electrode, the temperature rise rate, the roasting temperature, the roasting time, the reduction temperature and the reduction time in the preparation process of the electrode are limited, so that the loading capacity and the dispersity of ruthenium can be improved, and the loading stability and the catalytic activity of the ruthenium and the ionic conductor carrier can be enhanced.
4. The ruthenium-nickel composite electrode provided by the invention has better ammonia catalytic activity and electrochemical performance.
5. The electrode provided by the invention is applied to the direct ammonia SOFC, and can be used as the anode of the direct ammonia SOFC to improve the ammonia catalytic activity and the overall electrochemical performance of the direct ammonia SOFC.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The preparation method of the nickel-based electrode body comprises the following steps: uniformly mixing the first material and the second material according to the mass ratio, performing ball milling, performing dry pressing forming under 6-15 MPa, performing cold isostatic pressing under 200-300 MPa, and presintering at 500-600 ℃ for 5-10 hours under the air condition to obtain a nickel-based electrode body; in the following examples, the first material and the second material were mixed uniformly according to their mass ratio, ball-milled, dry-pressed at 10MPa, cold isostatic pressed at 200MPa, and then pre-fired at 550 ℃ for 10 hours under air conditions to obtain a nickel-based electrode body.
Example 1
The embodiment provides a method for preparing a ruthenium-nickel composite electrode, which comprises the following steps,
nickel-based electrode body (mass m) used in this example1) The material comprises a first material and a second material, wherein the first material is YSZ, the second material is nickel oxide, and the mass ratio of the first material to the second material is 4: 6; the content of ruthenium in the ruthenium-nickel composite electrode is 1 wt%;
the preparation method comprises the steps of preparing,
(1) weighing 0.3g of 5 wt% ruthenium nitrate solution, adding 0.3g of absolute ethyl alcohol, slightly shaking up to be used as a ruthenium precursor solution for later use, then dropwise coating the ruthenium precursor solution on a nickel-based electrode body, standing for 1h, and then drying for 1h at 100 ℃;
(2) heating to 450 ℃ at a heating rate of 1.2 ℃/min for roasting, cooling to room temperature after roasting for 20min to obtain the ruthenium oxide nickel-based composite electrode, wherein ruthenium oxide (RuO) can be generated in a ruthenium precursor solution in the roasting process2)；
(3) Weighing ruthenium oxideA nickel-based composite electrode having a mass of m2And (3) calculating the ruthenium content in the ruthenium oxide nickel-based composite electrode, and repeating the steps (1) and (2) until the ruthenium content in the nickel-based electrode body is 1 wt%, namely the ruthenium-based composite electrode satisfies the formula I:
(4) introducing hydrogen and reacting RuO at 800 deg.C2And reducing NiO into Ru and Ni respectively for 30min to obtain the ruthenium-nickel composite electrode;
the embodiment also provides a ruthenium-nickel composite electrode prepared by the method;
the ruthenium-nickel composite electrode can be used as an anode to be applied to a direct ammonia SOFC.
Example 2
The embodiment provides a method for preparing a ruthenium-nickel composite electrode, which comprises the following steps,
nickel-based electrode body (mass m) used in this example1) The material comprises a first material and a second material, wherein the first material is BCZY, the second material is nickel oxide, and the mass ratio of the first material to the second material is 7: 13; the content of ruthenium in the ruthenium-nickel composite electrode is 0.5 wt%;
the preparation method comprises the steps of preparing,
(1) weighing 0.05g of ruthenium chloride, adding 0.4g of deionized water, slightly shaking up to be used as a precursor solution of ruthenium for later use, then dropwise coating the precursor solution of ruthenium on a nickel-based electrode body, standing for 1.2h, and then drying for 0.4h at 120 ℃;
(2) heating to 500 ℃ at a heating rate of 1.0 ℃/min for roasting, cooling to room temperature after roasting for 15min to obtain the ruthenium oxide nickel-based composite electrode, wherein ruthenium oxide (RuO) can be generated in a ruthenium precursor solution in the roasting process2)；
(3) Weighing a ruthenium oxide nickel-based composite electrode with the mass m2And (3) calculating the ruthenium content in the ruthenium oxide nickel-based composite electrode, and repeating the steps (1) and (2) until the ruthenium content in the nickel-based electrode body is 0.5 wt%, so that the formula I is satisfied:
(4) introducing hydrogen and reacting RuO at 600 deg.C2And reducing NiO into Ru and Ni respectively for 2h to obtain the ruthenium-nickel composite electrode;
the embodiment also provides a ruthenium-nickel composite electrode prepared by the method;
the ruthenium-nickel composite electrode can be used as an anode to be applied to a direct ammonia SOFC.
Example 3
The embodiment provides a method for preparing a ruthenium-nickel composite electrode, which comprises the following steps,
nickel-based electrode body (mass m) used in this example1) The material comprises a first material and a second material, wherein the first material is GDC, the second material is nickel oxide, and the mass ratio of the first material to the second material is 9: 11; the ruthenium content in the ruthenium-nickel composite electrode is 3 wt%;
the preparation method comprises the steps of preparing,
(1) weighing 0.5g of ruthenium nitrate with the mass fraction of 5 wt%, adding 0.3g of absolute ethyl alcohol, slightly shaking up to be used as a precursor solution of ruthenium for later use, then dropwise coating the precursor solution of ruthenium on a nickel-based electrode body, standing for 0.5h, and then drying for 1.2h at 80 ℃;
(2) heating to 500 ℃ at a heating rate of 1.5 ℃/min for roasting, cooling to room temperature after roasting for 20min to obtain the ruthenium oxide nickel-based composite electrode, wherein ruthenium oxide (RuO) can be generated in a ruthenium precursor solution in the roasting process2)；
(3) Weighing a ruthenium oxide nickel-based composite electrode with the mass m2And (3) calculating the ruthenium content in the ruthenium oxide nickel-based composite electrode, and repeating the steps (1) and (2) until the ruthenium content in the nickel-based electrode body is 3wt%, namely the ruthenium-based composite electrode satisfies the formula I:
(4) introducing hydrogen and reacting RuO at 700 deg.C2And reducing NiO into Ru and Ni respectively for 1h to obtain the ruthenium-nickel composite electrode;
the embodiment also provides a ruthenium-nickel composite electrode prepared by the method;
the ruthenium-nickel composite electrode can be used as an anode to be applied to a direct ammonia SOFC.
Example 4
The embodiment provides a method for preparing a ruthenium-nickel composite electrode, which comprises the following steps,
nickel-based electrode body (mass m) used in this example1) The material comprises a first material and a second material, wherein the first material is BCZYYYb, the second material is nickel oxide, and the mass ratio of the first material to the second material is 6: 4; the ruthenium content in the ruthenium-nickel composite electrode is 2 wt%;
the preparation method comprises the steps of preparing,
(1) weighing 0.1g of ruthenium acetate, adding 0.4g of absolute ethyl alcohol, slightly shaking up to be used as a precursor solution of ruthenium for later use, then dropwise coating the precursor solution of ruthenium on a nickel-based electrode body, standing for 1.5h, and then drying for 0.8h at 90 ℃;
(2) heating to 480 ℃ at a heating rate of 1.3 ℃/min for roasting, cooling to room temperature after roasting for 30min to obtain the ruthenium oxide nickel-based composite electrode, wherein ruthenium oxide (RuO) can be generated from a ruthenium precursor solution in the roasting process2)；
(3) Weighing a ruthenium oxide nickel-based composite electrode with the mass m2And (3) calculating the ruthenium content in the ruthenium oxide nickel-based composite electrode, and repeating the steps (1) and (2) until the ruthenium content in the nickel-based electrode body is 2 wt%, namely the ruthenium content satisfies the formula I:
(4) introducing hydrogen and reacting RuO at 650 deg.C2And reducing NiO into Ru and Ni respectively for 1.5h to obtain the ruthenium-nickel composite electrode;
the embodiment also provides a ruthenium-nickel composite electrode prepared by the method;
the ruthenium-nickel composite electrode can be used as an anode to be applied to a direct ammonia SOFC.
Example 5
The embodiment provides a method for preparing a ruthenium-nickel composite electrode, which comprises the following steps,
nickel-based electrode body (mass m) used in this example1) The material comprises a first material and a second material, wherein the first material is BZY, the second material is nickel oxide, and the mass ratio of the first material to the second material is 3: 7; the ruthenium content in the ruthenium-nickel composite ammonia decomposition hydrogen production electrode is 2.5 wt%;
the preparation method comprises the steps of preparing,
(1) weighing 0.1g of ruthenium acetylacetonate, adding 0.3g of absolute ethyl alcohol, slightly shaking up to be used as a precursor solution of ruthenium for later use, dripping the precursor solution of ruthenium on a nickel-based electrode body, standing for 0.8h, and drying for 1h at 110 ℃;
(2) heating to 430 ℃ at a heating rate of 1.2 ℃/min for roasting, cooling to room temperature after roasting for 25min to obtain the ruthenium oxide nickel-based composite electrode, wherein ruthenium oxide (RuO) can be generated from a ruthenium precursor solution in the roasting process2)；
(3) Weighing a ruthenium oxide nickel-based composite electrode with the mass m2And (3) calculating the ruthenium content in the ruthenium oxide nickel-based composite electrode, and repeating the steps (1) and (2) until the ruthenium content in the nickel-based electrode body is 2.5 wt%, so that the formula I is satisfied:
(4) introducing hydrogen and reacting RuO at 600 deg.C2And reducing NiO into Ru and Ni respectively for 2h to obtain the ruthenium-nickel composite electrode;
the embodiment also provides a ruthenium-nickel composite electrode prepared by the method;
the ruthenium-nickel composite electrode can be used as an anode to be applied to a direct ammonia SOFC.
Test examples
The test example provides the electrochemical performance test and test results of the electrodes prepared in examples 1-5 as the anode electrode of the direct ammonia SOFC, and the specific test method is as follows, and the test results are shown in Table 1; blank group 1 is the nickel-based electrode body in the embodiment 1 as the anode electrode of the direct ammonia SOFC, and blank group 2 is the nickel-based electrode body in the embodiment 2 as the anode electrode of the direct ammonia SOFC;
the method of producing the direct ammonia SOFC in this test example includes the following steps,
preparation of electrolyte slurry and cathode slurry: mixing yttria-stabilized zirconia, nickel oxide and triethanolamine, and performing ball milling to obtain electrolyte slurry; mixing lanthanum strontium manganese, terpineol and ethyl cellulose, and performing ball milling to obtain cathode slurry;
preparation of direct ammonia SOFC: uniformly coating the electrolyte slurry on an anode electrode by adopting a spin coating method to obtain an anode support body with an electrolyte film structure, then roasting for 10 hours at 1200 ℃ in the air to form an electrolyte film, then coating the cathode slurry on the electrolyte film by adopting a screen printing method, drying, and roasting for 4 hours at 1100 ℃ to form a cathode electrode; then the solid is placed in a hydrogen atmosphere and reduced at 700 ℃ to obtain the direct ammonia SOFC.
The electrochemical performance test method comprises the following steps: 20mL/min ammonia is directly introduced into the anode of the ammonia SOFC, 50mL/min air is introduced into the cathode, and the corresponding current value of the SOFC at 600 ℃ and 0.7V is tested, wherein the larger the current value is, the better the electrochemistry is;
the method for testing the ammonia decomposition efficiency comprises the following steps: testing the concentration of ammonia at the outlet under the ammonia flow of 20mL/min under the open circuit voltage by chromatography;
table 1 results of performance test of electrodes prepared in examples 1 to 2 and comparative example 1
| Examples of the invention | Electrochemical Properties (A) | Efficiency of Ammonia decomposition (%) |
| Blank group 1 | 0.48 | 21 |
| Blank group 2 | 0.65 | 36 |
| Example 1 | 0.55 | 53 |
| Example 2 | 0.96 | 72 |
| Example 3 | 0.75 | 58 |
| Example 4 | 0.78 | 62 |
| Example 5 | 0.80 | 63 |
In table 1, example 1 shows that the electrochemical performance and ammonia decomposition efficiency of the electrode prepared in this example are better than those of blank 1; example 2 compared with blank group 2, the electrochemical performance and ammonia decomposition efficiency of the electrode prepared in the example are better; the electrochemical performance and ammonia decomposition efficiency of the electrodes prepared in examples 3 to 5 were good.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of a ruthenium-nickel composite electrode is characterized by comprising the following steps,
(1) dripping a precursor solution of ruthenium on a nickel-based electrode body, standing and drying;
(2) sequentially roasting and cooling the nickel-based electrode body to prepare a ruthenium oxide nickel-based composite electrode;
(3) weighing and calculating the ruthenium content in the ruthenium oxide nickel-based composite electrode, and repeating the steps (1) and (2) until the ruthenium content in the nickel-based electrode body is 0.5-3 wt%;
(4) and (4) reducing the ruthenium oxide nickel-based composite electrode treated in the step (3) to obtain the ruthenium-nickel composite electrode.
2. The method according to claim 1, wherein the nickel-based electrode body comprises an electrode sheet and an electrolyte layer provided thereon, wherein the electrolyte layer comprises a first material and a second material, and the first material is one of barium-based perovskite, zirconia-based rare earth metal oxide, cerium oxide-based rare earth metal oxide, lanthanum gallate-based perovskite; the second material is a nickel source;
the zirconia-based rare earth metal oxide is yttria-stabilized zirconia or scandia-stabilized zirconia;
the cerium oxide-based rare earth metal oxide is gadolinium-doped cerium oxide or strontium-doped cerium oxide;
the barium-based perovskite is zirconium yttrium doped barium cerate, zirconium yttrium ytterbium doped barium cerate or yttrium doped barium zirconate;
the lanthanum gallate-based perovskite is lanthanum gallate doped with zirconium, strontium and magnesium.
3. The method of claim 2, wherein the mass ratio of the first material to the second material is 3:7 to 6: 4.
4. The production method according to any one of claims 1 to 3, wherein the precursor in the ruthenium precursor solution is at least one of ruthenium chloride, ruthenium nitrate, ruthenium acetate, or ruthenium acetylacetonate;
the solvent of the precursor solution of ruthenium is water or ethanol; the mass fraction of the precursor in the precursor solution of ruthenium is 3-15%.
5. The production method according to any one of claims 1 to 3, wherein the standing time is 0.5 to 1.5 hours;
the drying temperature is 80-120 ℃, and the drying time is 0.4-1.2 h.
6. The method according to any one of claims 1 to 3, wherein the calcination temperature is 400-500 ℃, and the calcination time is 15-30 min.
7. The method as claimed in any one of claims 1 to 3, further comprising a step of raising the temperature of the nickel-based electrode body to 400-500 ℃ at a temperature raising rate of 1-1.5 ℃/min before the firing.
8. The production method according to any one of claims 1 to 3, wherein the reduction is carried out by placing the ruthenium oxide nickel-based composite electrode treated in the step (3) in a hydrogen atmosphere;
the temperature of the reduction is 600-800 ℃, and the time is 0.5-2 h.
9. A ruthenium-nickel composite electrode, characterized by being produced by the production method according to any one of claims 1 to 8.
10. The application of the ruthenium-nickel composite electrode in a direct ammonia solid oxide fuel cell is characterized in that the ruthenium-nickel composite electrode is the ruthenium-nickel composite electrode according to claim 9 or is obtained by the preparation method according to any one of claims 1 to 8.
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|---|
| Catalytic ammonia decomposition for hydrogen production on Ni, Ru and Ni-Ru supported on CeO2;Ilaria Lucentini 等;《International Journal of Hydrogen Energy》;20190208;第44卷;全文 * |
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