CN117497785A - Fuel cell anode material and preparation method and application thereof - Google Patents

Fuel cell anode material and preparation method and application thereof Download PDF

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Publication number
CN117497785A
CN117497785A CN202311852462.1A CN202311852462A CN117497785A CN 117497785 A CN117497785 A CN 117497785A CN 202311852462 A CN202311852462 A CN 202311852462A CN 117497785 A CN117497785 A CN 117497785A
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China
Prior art keywords
anode material
fuel cell
source
preparing
cell anode
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CN202311852462.1A
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Chinese (zh)
Inventor
邹才能
张宇轩
王建强
杨征
程付鹏
李海龙
闵洛夫
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Petrochina Shenzhen New Energy Research Institute Co ltd
Petrochina Co Ltd
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Petrochina Shenzhen New Energy Research Institute Co ltd
Petrochina Co Ltd
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Priority to CN202311852462.1A priority Critical patent/CN117497785A/en
Publication of CN117497785A publication Critical patent/CN117497785A/en
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/30—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/11—Sulfides
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • 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
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The application relates to a fuel cell anode material, a preparation method and application thereof, belonging to the technical field of fuel cells; the method comprises the following steps: dissolving a sulfur source, urea and a metal source in a solvent to obtain a mixed solution; carrying out hydrothermal reaction on the mixed solution to form a metal fluidization substance, thereby obtaining an anode material; the method can simply and rapidly prepare the metal sulfide through a hydrothermal method, and the metal sulfide can stably exist in the hydrogen sulfide atmosphere for a long time, so that hydrogen sulfide is not poisoned, and the concern of performance attenuation does not exist; the catalyst can be used as an anode material of a fuel cell and can be applied to sulfur-containing fuels. Meanwhile, based on the characteristic that sulfide can catalyze and decompose hydrogen sulfide, the output performance of the whole battery can be obviously improved even if the fuel gas contains hydrogen sulfide.

Description

Fuel cell anode material and preparation method and application thereof
Technical Field
The application relates to the technical field of fuel cells, in particular to a fuel cell anode material and a preparation method and application thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is an electrochemical device that is capable of directly converting chemical fuel into electrical energy. Compared with other power generation technologies, the power generation system has the advantages of high efficiency, modularization, reliability, environmental protection and the like. However, the most widely used SOFC anode material at present, nickel-stabilized zirconia (Ni-YSZ) cermet, is H-present 2 S poisoning problem: at 800℃when 2.5ppmH was added to the feed gas 2 At S, the electrochemical performance was reduced by 12.5%. H in most conventional fuels (e.g. gas, biogas, petroleum gas, natural gas, etc) 2 The concentration of S is typically higher than ppm. These levels of H 2 The S content is sufficient to impair the performance of the nickel anode cell in a short time. Therefore, there is an urgent need to develop SOFC anode materials that are catalytically active in sulfur-containing fuels and have chemical and electrochemical stability.
Disclosure of Invention
The application provides a fuel cell anode material, a preparation method and application thereof, so as to solve the problem that the prior anode is not suitable for sulfur-containing fuel.
In a first aspect, the present application provides a method for preparing a fuel cell anode material, the method comprising:
dissolving a sulfur source, urea and a metal source in a solvent to obtain a mixed solution;
and carrying out hydrothermal reaction on the mixed solution to form metal fluidization matters, thereby obtaining the anode material.
As an alternative embodiment, the sulfur source comprises thioacetamide.
As an alternative embodiment, the metal source includes a cobalt source and a nickel source.
As an alternative embodiment, the cobalt source and nickel source are nitrates.
As an alternative embodiment, the cobalt source comprises Co (NO 3 ) 2 。
As an alternative embodiment, the nickel source comprises Ni (NO 3 ) 2 。
As an optional embodiment, the mass ratio of the sulfur source, urea, cobalt source and nickel source is (1-3): (2-4): (1-2): (1-2).
As an optional embodiment, the mass ratio of the sulfur source, urea, cobalt source and nickel source is (1.5-2.5): (2.5 to 3.5): (1.2 to 1.8): (1.2-1.8).
As an optional embodiment, the mass ratio of the sulfur source, urea, cobalt source and nickel source is (1.9-2.3): (2.8-3.2): (1.4 to 1.5): (1.4 to 1.5).
As an alternative embodiment, the solvent comprises deionized water.
As an alternative embodiment, the relationship of the dissolution of the sulfur source in the solvent satisfies: 1-3 g of sulfur source is dissolved in each 50 mL.
As an optional implementation manner, the temperature of the hydrothermal reaction is 120-200 ℃; and/or
The hydrothermal reaction time is 18-30 hours.
As an optional implementation manner, the temperature of the hydrothermal reaction is 140-180 ℃; and/or
The hydrothermal reaction time is 20-28 hours.
As an optional implementation manner, the temperature of the hydrothermal reaction is 150-170 ℃; and/or
The hydrothermal reaction time is 22-26 hours.
In a second aspect, the present application provides a fuel cell anode material prepared by the preparation method of the first aspect.
As an alternative embodiment, the anode material comprises a metal sulfide.
As an alternative embodiment, the metal sulfide includes M 9 S 8 Wherein M comprises Co and/or Ni.
As an alternative embodiment, the anode material further comprises MoS 2 And stabilized zirconia (YSZ for short).
In a third aspect, the present application provides the use of an anode material for a fuel cell, the anode material being produced by the production method of the first aspect, the use comprising applying the anode material to a fuel cell for supplying hydrogen sulphide containing gas.
As an alternative embodiment, the hydrogen sulfide is present in the feed gas in a volume ratio of at least 50ppm.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the method provided by the embodiment of the application, the metal sulfide can be simply and rapidly prepared by a hydrothermal method, and can be stably existing in the hydrogen sulfide atmosphere for a long time, so that hydrogen sulfide is not poisoned, and the concern of performance attenuation does not exist; the catalyst can be used as an anode material of a fuel cell and can be applied to sulfur-containing fuels. Meanwhile, based on the characteristic that sulfide can catalyze and decompose hydrogen sulfide, the output performance of the whole battery can be obviously improved even if the fuel gas contains hydrogen sulfide.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a flow chart of a method provided by an embodiment of the present application;
FIG. 2 is a graph showing XRD results of the anode material provided in example 1 of the present application after having been incubated for a period of time under different atmospheres;
FIG. 3 shows the electrochemical performance of a full cell made of the anode material provided in example 1 of the present application under different atmospheres;
FIG. 4 is a graph showing the results of stability testing of the anode material provided in example 1 of the present application for a full cell;
fig. 5 is a graph showing the performance of the anode material prepared in example 1 of the present application before and after the stability test.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods.
A Solid Oxide Fuel Cell (SOFC) is an electrochemical device that is capable of directly converting chemical fuel into electrical energy. Compared with other power generation technologies, the power generation system has the advantages of high efficiency, modularization, reliability, environmental protection and the like. However, the most widely used at presentSOFC anode material- -Nickel-stabilized zirconia (Ni-YSZ) cermet presents H 2 S poisoning problem: at 800℃when 2.5ppmH was added to the feed gas 2 At S, the electrochemical performance was reduced by 12.5%. H in most conventional fuels (e.g. gas, biogas, petroleum gas, natural gas, etc) 2 The concentration of S is typically higher than ppm. These levels of H 2 The S content is sufficient to impair the performance of the nickel anode cell in a short time. Therefore, there is an urgent need to develop SOFC anode materials that are catalytically active in sulfur-containing fuels and have chemical and electrochemical stability.
Metal sulfides have good conductivity and are commonly used in semiconductors in the prior art. For example taiwan patent application TW20180132993, which discloses a method for depositing metal chalcogenides (Chalcogenide) on a substrate by cyclical deposition, and in particular, relates to cyclical deposition of Tin disulfide (Tin distulfide) or germanium disulfide (Germanium disulfide). The invention also relates to semiconductor device structures containing metal chalcogenide thin films formed using cyclical deposition. The as-deposited metal chalcogenide film may be at least partially crystalline, but crystallization of the metal chalcogenide film may proceed slowly during the deposition process, such that thinner films are less crystalline than thicker films. This can be a problem when the metal chalcogenide thin film comprises a 2D material that is less than about 10 nanometers thick. Thus, in certain embodiments of the invention, the as-deposited metal chalcogenide thin film may be subjected to a post deposition annealing process to improve the crystallinity of the metal chalcogenide thin film. For example, in certain embodiments, the method of depositing a metal chalcogenide may also further comprise a post deposition anneal of the metal chalcogenide at a temperature between about 150 ℃ and about 300 ℃. In certain embodiments, the annealing treatment of the metal chalcogenide may include heating the metal chalcogenide to a temperature of about less than 800 ℃, about less than 600 ℃, about less than 500 ℃, or even about less than 400 ℃. In certain embodiments, the post-deposition anneal of the metal chalcogenide thin film may be performed in an atmosphere comprising a chalcogen element, e.g., the post-deposition anneal process may be performed in an environment comprising a chalcogenide compound, e.g., a sulfur compound, such as hydrogen sulfide (H) 2 S) atmosphere. In certain embodiments, the post deposition annealing treatment of the metal chalcogenide thin film may be performed for a period of time of less than 1 hour, or less than 30 minutes, or less than 15 minutes, or even less than 5 minutes. In certain embodiments, the post deposition anneal of the metal chalcogenide film (such as a tin disulfide film) may be performed in an atmosphere that does not contain chalcogen (such as S, se or Te), for example in an inert gas atmosphere (such as N 2 ) Inert gases (such as Ar or He) or in hydrogen-containing environments (such as H 2 Or H 2 /N 2 An environment).
The inventors have found that the metal sulfides also have good catalytic activity, such as pentlandite M 9 S 8 (wherein M can be a mixture of Fe, co or Ni, etc.), and has been widely used in the fields of energy storage and conversion devices such as supercapacitors, lithium ion batteries, solar cells, etc., because of its excellent electrocatalytic properties, environmental protection, low cost, and abundant resources. When the catalyst is used as an anode of a solid oxide fuel cell, the catalyst is contained in a fuel gas in an amount of 50 ppmH 2 When S, the output performance of the full battery is not reduced, but a certain improvement appears, and meanwhile, the full battery can stably run for a period of time. It has the prospect of being used as a sulfur-containing fuel conversion anode catalyst of a solid oxide fuel cell.
The inventors have intended the preparation of nickel pyrite (Co, ni) by hydrothermal method 9 S 8 And is used for containing H in fuel gas 2 S solid oxide fuel cell anode.
As shown in fig. 1, an embodiment of the present application provides a method for preparing a fuel cell anode material, including:
s1, dissolving a sulfur source, urea and a metal source in a solvent to obtain a mixed solution;
the sulfur source refers to a substance capable of providing sulfur ions during the hydrothermal reaction. Urea (urea), also known as urea, carboxamide, of the formula CH 4 N 2 O or CO (NH) 2 ) 2 Is an organic compound composed of carbon, nitrogen, oxygen and hydrogen, and is a white crystal. The metal source refers to a substance capable of providing metal ions during the hydrothermal reaction. Specific metal ionsAnd can be selected according to practical needs, such as cobalt ions, nickel ions and the like.
A Solvent (Solvent) is a liquid (gas, or solid) that can solubilize a solid, liquid, or gaseous solute (both solvents and solutes can be solid, liquid, gas), which in turn becomes a solution. The most common solvent in everyday life is water. The organic solvent is an organic compound containing a carbon atom. Solvents generally possess relatively low boiling points and are readily volatile. Or may be removed by distillation, leaving behind the solubles. Thus, the solvent may not chemically react with the solute.
In some embodiments, the sulfur source comprises thioacetamide; the metal source comprises a cobalt source and a nickel source, the cobalt source and the nickel source are nitrate, and the solvent comprises deionized water. Further, the cobalt source comprises Co (NO 3 ) 2 The nickel source comprises Ni (NO 3 ) 2 。
In some embodiments, the mass ratio of the sulfur source, urea, cobalt source and nickel source is (1-3): (2-4): (1-2): (1-2). Further, the mass ratio of the sulfur source to the urea to the cobalt source to the nickel source is (1.5-2.5): (2.5 to 3.5): (1.2 to 1.8): (1.2-1.8). Further, the mass ratio of the sulfur source to the urea to the cobalt source to the nickel source is (1.9-2.3): (2.8-3.2): (1.4 to 1.5): (1.4 to 1.5). Exemplary, the mass ratio of the sulfur source, urea, cobalt source, and nickel source is 1:2:1:1. 1.5:2:1: 1. 2:2:1: 1. 2.5:2:1: 3. 1:2:1:1. 1:2.5:1: 1. 1:3:1: 1. 1:3.5:1: 1. 1:4:1: 1. 1:2:1.5: 1. 1:2:2: 1. 1:2:1:1.5 or 1:2:1:2, etc., which may be (1 to 3): (2-4): (1-2): any value within the range of (1-2).
In some embodiments, the relationship of the sulfur source dissolved in the solvent satisfies: 1-3 g of sulfur source is dissolved in each 50 mL. Illustratively, the relationship of the dissolution of the sulfur source in the solvent may be: 1g of sulfur source is dissolved per 50mL, 1.2g of sulfur source is dissolved per 50mL, 1.4g of sulfur source is dissolved per 50mL, 1.6g of sulfur source is dissolved per 50mL, 1.8g of sulfur source is dissolved per 50mL, 2g of sulfur source is dissolved per 50mL, 2.2g of sulfur source is dissolved per 50mL, 2.4g of sulfur source is dissolved per 50mL, 2.6g of sulfur source is dissolved per 50mL, 2.8g of sulfur source is dissolved per 50mL, or 3g of sulfur source is dissolved per 50mL, and any value within the range of 1-3 g of sulfur source is dissolved per 50 mL.
Specifically, in this example, thioacetamide (2.104, g) was used as a sulfur source, and urea (3.000, g), co (NO 3 ) 2 (1.455. 1.455 g) and Ni (NO) 3 ) 2 (1.455. 1.455 g) were dissolved together in 50ml of deionized water to obtain a mixed solution.
S2, carrying out hydrothermal reaction on the mixed solution to form a metal fluidization substance, and obtaining the anode material.
The hydrothermal reaction is usually carried out in a hydrothermal synthesis reaction kettle, which is also called a polymerization reaction kettle, a high-pressure digestion tank, a hydrothermal reaction kettle, a pressure bomb and a digestion tank. The hydrothermal synthesis reaction kettle is a closed container capable of decomposing insoluble substances. The method can be used for sample pretreatment in analysis such as atomic absorption spectrum and plasma emission; can also be used for small-dose synthetic reactions; the aim of rapidly resolving insoluble substances can be achieved by utilizing a strong acid or strong alkali in the tank body and a high-temperature high-pressure closed environment.
In some embodiments, the temperature of the hydrothermal reaction is 120-200 ℃; the hydrothermal reaction time is 18-30 hours. Further, the temperature of the hydrothermal reaction is 140-180 ℃; the hydrothermal reaction time is 20-28 hours. Further, the temperature of the hydrothermal reaction is 150-170 ℃; the hydrothermal reaction time is 22-26 hours. The temperature of the hydrothermal reaction may be 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, or the like, and may be any value within the range of 120 to 200 ℃. The time of the hydrothermal reaction may be 18 hours, 18.5 hours, 19 hours, 19.5 hours, 20 hours, 20.5 hours, 21 hours, 21.5 hours, 22 hours, 22.5 hours, 23 hours, 23.5 hours, 24 hours, 24.5 hours, 25 hours, 25.5 hours, 26 hours, 26.5 hours, 27 hours, 27.5 hours, 28 hours, 28.5 hours, 29 hours, 29.5 hours, 30 hours, or the like, and may be any value within a range of 18 to 30 hours.
Specifically, in this example, the solution was transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 160 ℃ and heated for 24 hours. And cooling, taking out, filtering or centrifuging to obtain black precipitate, namely the anode material.
The method can simply and rapidly prepare the metal sulfide through a hydrothermal method, and the metal sulfide can stably exist in the hydrogen sulfide atmosphere for a long time, cannot poison hydrogen sulfide and has no problem of performance attenuation; therefore, the catalyst can be used as an anode material of a fuel cell and can be applied to sulfur-containing fuels. Meanwhile, based on the characteristic that sulfide can catalyze and decompose hydrogen sulfide, the output performance of the whole battery can be obviously improved even if the fuel gas contains hydrogen sulfide.
Based on one general inventive concept, embodiments of the present application also provide a fuel cell anode material manufactured using the manufacturing method provided above.
The anode material is prepared based on the above method, and specific steps of the method can refer to the above embodiment, and because the anode material adopts some or all of the technical solutions of the above embodiment, at least the anode material has all the beneficial effects brought by the technical solutions of the above embodiment, and will not be described in detail herein.
Unlike the Ni anode reacts with hydrogen sulfide in the hydrogen sulfide-containing atmosphere, which results in the decline of the output performance of the whole cell, the anode material is not only not poisoned by hydrogen sulfide, but also can catalyze and decompose hydrogen sulfide, so when the metal sulfide is used as the anode of the solid oxide fuel cell, when the fuel gas contains hydrogen sulfide, the performance is improved to a certain extent, and the anode material can stably operate for a long time in the hydrogen sulfide-containing atmosphere.
In some embodiments, the anode material comprises a metal sulfide. Further, the metal sulfide includes M 9 S 8 Wherein M comprises Co and/or Ni.
In some embodiments, the anode material further comprises MoS 2 And stabilized zirconia (YSZ for short).
Based on one general inventive concept, embodiments of the present application also provide a use of the anode material for a fuel cell, the anode material being prepared using the preparation method provided above, the use comprising applying the anode material to a fuel cell for supplying hydrogen sulfide.
The application is realized based on the above method, and specific steps of the method can refer to the above embodiment, and because the application adopts some or all of the technical solutions of the above embodiment, at least the application has all the beneficial effects brought by the technical solutions of the above embodiment, and will not be described in detail herein.
Specifically, in the present embodiment, the assembly process of the fuel cell including the anode of the anode material includes: firstly preparing a compact electrolyte supporting layer, pressing uniformly mixed stable zirconia (YSZ for short) powder and 3 wt% polyvinyl butyral (PVB) into a die by adopting a dry pressing method, heating at 1450 ℃ for 5 hours, and sintering to obtain the compact stable zirconia (YSZ for short) wafer supporting body. The anode of the single battery consists of 70% La 0.7 Sr 0.3 MnO 3 (LSM, ningbo SOFCMAN energy technologies Co.) was mixed with 30% YSZ, screen printed and sintered at 1200deg.C for 3 hours. The anode is screen printed on the other side of the electrolyte support layer. The current collector layer Pt is attached to the electrode surface by drawing a mesh pattern and connected by two Au wires.
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
The reagents in the examples below were purchased from the national drug group. The reagent purchased was AR-grade in purity and no additional purification work was performed.
Example 1
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (2.104, g) is used as sulfur source, and is mixed with urea (3.000, g), co (NO) 3 ) 2 (1.455. 1.455 g) and Ni (NO) 3 ) 2 (1.455. 1.455 g) together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 160 ℃ and heated for 24 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
For example 1 (Co, ni) 9 S 8 XRD testing was performed, which included XRD testing after storage in an argon atmosphere at various temperatures for a period of time and at 50ppm H 2 Performing XRD test after the S is preserved for a period of time at 800 ℃ in the hydrogen atmosphere; the results are shown in FIG. 2, FIG. 2 is a graph showing XRD results of the anode material provided in example 1 of the present application after having been incubated for a period of time under different atmospheres, as can be seen from the graph, (Co, ni) 9 S 8 The sample had small amounts of other sulfide impurities formed in an argon atmosphere, but contained 50ppm H 2 The hydrogen of S can keep good phase purity, which indicates (Co, ni) 9 S 8 Can be stably present in 50ppm H 2 S in hydrogen.
Prepared in example 1 (Co, ni) 9 S 8 And MoS 2 Stabilized zirconia (YSZ for short) as anode material (Co, ni) 9 S 8 -MoS 2 YSZ and evaluating its electrochemical performance and sulfur resistance as anode for solid oxide fuel cells.
The solid oxide fuel cell assembly process is as follows: firstly, preparing a compact electrolyte supporting layer, pressing the uniformly mixed YSZ powder and 3 wt% PVB (polyvinyl butyral) into a die by adopting a dry pressing method, and heating at 1450 ℃ for 5 hours to sinter to obtain the compact YSZ wafer supporting body. The anode of the single battery consists of 70% La 0.7 Sr 0.3 MnO 3 (LSM, ningbo SOFCMAN energy technologies Co.) was mixed with 30% YSZ, screen printed and sintered at 1200deg.C for 3 hours. The anode is arranged on the other side of the electrolyte supporting layerAnd (5) performing line screen printing. The current collector layer Pt is attached to the electrode surface by drawing a mesh pattern and connected by two Au wires.
The electrochemical performance of the battery piece manufactured by the method is tested, and the testing process comprises the following steps: the battery piece is fixed at one end of a double-pass quartz tube with the same size as the battery piece by ceramic glue, and is put into a tube furnace, and nitrogen is respectively injected into the anode chamber and the cathode chamber before testing. The tube furnace was warmed to the test temperature (750 ℃, 800 ℃ and 850 ℃). At the test temperature, N 2 Is switched to contain 50ppm H 2 S hydrogen or pure hydrogen. As a result, as shown in fig. 3, fig. 3 shows electrochemical properties of the full cell made of the anode material provided in example 1 of the present application under different atmospheres, and it should be noted that the direction of the arrow in the figure is the axis coordinate read corresponding to the curve; as can be seen from the figure, the composition contains 50ppm H in use 2 When S hydrogen is used as fuel gas, the electrochemical performance of the full cell is obviously improved, which indicates that H 2 S not only does not damage the battery performance, but also improves the battery performance.
The stability test is carried out on the battery piece manufactured by the method, the test process comprises the steps of fixing the battery piece at one end of a double-pass quartz tube with the same size as the battery piece by ceramic glue, putting the battery piece into a tube furnace, and injecting nitrogen into an anode chamber and a cathode chamber before the test. The tube furnace was warmed to the test temperature (850 ℃). At the test temperature, N 2 Is switched to contain 50ppm H 2 S, continuously carrying out long-term stability test for 100min, wherein the result is shown in FIG. 4, and FIG. 4 is a graph of the stability test result of the full cell made of the anode material provided in embodiment 1 of the present application, and it should be noted that the direction of an arrow in the graph is the axis coordinate read correspondingly to the curve; as can be seen from the figure, the catalyst contains 50ppm H 2 In the long-term stability test of 100min under the atmosphere of S hydrogen, the performance is not basically attenuated, which indicates that the full cell performance is not subjected to H 2 S is damaged, so that the output performance can be stabilized.
The results of comparing the performance of the battery piece before and after stability are shown in fig. 5, and fig. 5 is a graph showing the performance of the whole battery made of the anode material provided in embodiment 1 of the present application before and after stability test, and it should be noted that the direction of the arrow in the graph is the axis coordinate read correspondingly to the curve; as can be seen from the graph, the performance output of the battery was not substantially changed after the stability test, and was substantially consistent with the performance before the stability test.
Example 2
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (2.104, g) is used as sulfur source, and is mixed with urea (3.000, g), co (NO) 3 ) 2 (1.455. 1.455 g) and Ni (NO) 3 ) 2 (1.455. 1.455 g) together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 120 ℃ and heated for 30 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 3
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (2.104, g) is used as sulfur source, and is mixed with urea (3.000, g), co (NO) 3 ) 2 (1.455. 1.455 g) and Ni (NO) 3 ) 2 (1.455. 1.455 g) together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 200 ℃ and heated for 18 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 4
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (2.104, g) is used as sulfur source, and is mixed with urea (3.000, g), co (NO) 3 ) 2 (1.455. 1.455 g) and Ni (NO) 3 ) 2 (1.455. 1.455 g) together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 140 ℃ and heated for 28 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 5
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (2.104, g) is used as sulfur source, and is mixed with urea (3.000, g), co (NO) 3 ) 2 (1.455. 1.455 g) and Ni (NO) 3 ) 2 (1.455. 1.455 g) together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 180 ℃ and heated for 20 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 6
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (2.104, g) is used as sulfur source, and is mixed with urea (3.000, g), co (NO) 3 ) 2 (1.455. 1.455 g) and Ni (NO) 3 ) 2 (1.455. 1.455 g) together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 150 ℃ and heated for 26 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 7
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (2.104, g) is used as sulfur source, and is mixed with urea (3.000, g), co (NO) 3 ) 2 (1.455. 1.455 g) and Ni (NO) 3 ) 2 (1.455. 1.455 g) together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 170 ℃ and heated for 22 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 8
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (1 g) is used as sulfur source, and is mixed with urea (2 g), co (NO) 3 ) 2 (1g) And Ni (NO) 3 ) 2 (1g) Together dissolved in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle,screw down and place in an oven at 160 ℃ for 24 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 9
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (3 g) is used as sulfur source, and is mixed with urea (3 g), co (NO) 3 ) 2 (2g) And Ni (NO) 3 ) 2 (2g) Together dissolved in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 160 ℃ and heated for 24 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 10
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (1.5 g) was used as sulfur source, and urea (2.5. 2.5 g), co (NO) 3 ) 2 (1.2 g) and Ni (NO) 3 ) 2 (1.2 g) were dissolved together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 160 ℃ and heated for 24 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 11
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (2.5. 2.5 g) is used as sulfur source, and is mixed with urea (3.5. 3.5 g), co (NO) 3 ) 2 (1.8 g) and Ni (NO) 3 ) 2 (1.8 g) were dissolved together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 160 ℃ and heated for 24 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 12
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (1.9 g) was used as a sulfur source in combination withUrea (2.8 g), co (NO) 3 ) 2 (1.4. 1.4 g) and Ni (NO) 3 ) 2 (1.4 g) were dissolved together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 160 ℃ and heated for 24 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Example 13
A method of preparing a fuel cell anode material, the method comprising:
thioacetamide (2.3 g) is used as sulfur source, and urea (3.2 g), co (NO) 3 ) 2 (1.5 g) and Ni (NO) 3 ) 2 (1.5 g) were dissolved together in 50ml deionized water. The solution was then transferred to a 100ml polytetrafluoroethylene tank hydrothermal kettle, screwed up and placed in an oven at 160 ℃ and heated for 24 hours. Cooling, taking out, filtering or centrifuging to obtain black precipitate (Co, ni) 9 S 8 。
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the terms "include", "comprise", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (20)

1. A method of preparing a fuel cell anode material, the method comprising:
dissolving a sulfur source, urea and a metal source in a solvent to obtain a mixed solution;
and carrying out hydrothermal reaction on the mixed solution to form metal fluidization matters, thereby obtaining the anode material.
2. The method of producing a fuel cell anode material according to claim 1, wherein the sulfur source comprises thioacetamide.
3. The method of preparing a fuel cell anode material according to claim 1, wherein the metal source comprises a cobalt source and a nickel source.
4. A method of preparing a fuel cell anode material according to claim 3, wherein the cobalt source and nickel source are nitrates.
5. The method for preparing anode material for fuel cell according to claim 4, wherein the cobalt source comprises Co (NO 3 ) 2 。
6. The method for producing a fuel cell anode material according to claim 4, wherein the nickel source comprises Ni (NO 3 ) 2 。
7. The method for preparing a fuel cell anode material according to claim 3, wherein the mass ratio of the sulfur source, urea, cobalt source and nickel source is (1-3): (2-4): (1-2): (1-2).
8. The method for preparing a fuel cell anode material according to claim 7, wherein the mass ratio of the sulfur source, urea, cobalt source and nickel source is (1.5-2.5): (2.5 to 3.5): (1.2 to 1.8): (1.2-1.8).
9. The method for preparing a fuel cell anode material according to claim 7, wherein the mass ratio of the sulfur source, urea, cobalt source and nickel source is (1.9-2.3): (2.8-3.2): (1.4 to 1.5): (1.4 to 1.5).
10. The method of preparing a fuel cell anode material according to claim 1, wherein the solvent comprises deionized water.
11. The method for producing a fuel cell anode material according to claim 1, wherein the relationship of the dissolution of the sulfur source in the solvent satisfies: 1-3 g of sulfur source is dissolved in each 50 mL.
12. The method for preparing the anode material of the fuel cell according to claim 1, wherein the temperature of the hydrothermal reaction is 120-200 ℃; and/or
The hydrothermal reaction time is 18-30 hours.
13. The method for preparing a fuel cell anode material according to claim 12, wherein the temperature of the hydrothermal reaction is 140-180 ℃; and/or
The hydrothermal reaction time is 20-28 hours.
14. The method for preparing a fuel cell anode material according to claim 13, wherein the temperature of the hydrothermal reaction is 150-170 ℃; and/or
The hydrothermal reaction time is 22-26 hours.
15. A fuel cell anode material, characterized in that the anode material is produced by the production method according to any one of claims 1 to 14.
16. The fuel cell anode material of claim 15, wherein the anode material comprises a metal sulfide.
17. The fuel cell anode material of claim 15, wherein the metal sulfide comprises M 9 S 8 Wherein M comprises Co and/or Ni.
18. The fuel cell anode material of claim 15, wherein the anode material further comprises MoS 2 And stabilizing zirconia.
19. Use of the anode material of a fuel cell, wherein the anode material is produced by the production method according to any one of claims 1 to 14, comprising applying the anode material to a fuel cell for supplying hydrogen sulfide.
20. The use of fuel cell anode material according to claim 19, wherein the hydrogen sulphide has a volume fraction in the feed gas of at least 50ppm.
CN202311852462.1A 2023-12-29 2023-12-29 Fuel cell anode material and preparation method and application thereof Pending CN117497785A (en)

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