CN116864704B - Anode material of fuel cell, preparation method thereof, fuel cell and anode thereof - Google Patents
Anode material of fuel cell, preparation method thereof, fuel cell and anode thereof Download PDFInfo
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- CN116864704B CN116864704B CN202311131910.9A CN202311131910A CN116864704B CN 116864704 B CN116864704 B CN 116864704B CN 202311131910 A CN202311131910 A CN 202311131910A CN 116864704 B CN116864704 B CN 116864704B
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- 239000000446 fuel Substances 0.000 title claims abstract description 90
- 239000010405 anode material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 67
- 150000003839 salts Chemical class 0.000 claims abstract description 62
- 238000002156 mixing Methods 0.000 claims abstract description 47
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 44
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 44
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 32
- 239000000376 reactant Substances 0.000 claims abstract description 32
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 22
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 22
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 22
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000004321 preservation Methods 0.000 claims abstract description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 13
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 13
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000002815 nickel Chemical group 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 12
- 238000005245 sintering Methods 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 8
- 238000007650 screen-printing Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
Abstract
The application relates to the technical field of fuel cells, in particular to an anode material of a fuel cell, a preparation method thereof, the fuel cell and an anode thereof, and aims to solve the technical problems that the prepared anode is low in density and the conductivity does not meet the requirement in the preparation process of the anode of the fuel cell, wherein the preparation method comprises the following steps: preparing a molten salt solvent, wherein the components of the molten salt solvent comprise sodium nitrate, potassium nitrate and lithium nitrate; preparing a reaction reagent, wherein the components of the reaction reagent comprise zirconium nitrate, yttrium oxide and nickel nitrate; mixing molten salt solvent and a reaction reagent on a mixer; carrying out heat preservation treatment on the mixed molten salt solvent and the reactant so as to enable the reactant to react and generate anode materials of the fuel cell; the anode material of the fuel cell is separated through the steps of centrifugation, filtration and drying, and the anode powder prepared by the molten salt method is different from the traditional sintering method, and has the advantages of simple preparation process and high conductivity.
Description
Technical Field
The application relates to the technical field of fuel cells, in particular to an anode material of a fuel cell, a preparation method of the anode material, the fuel cell and an anode of the fuel cell.
Background
In the preparation process of the fuel cell anode in the related technology, the preparation process is generally complex, the prepared anode has lower density, and the conductivity does not meet the requirement.
Therefore, the application discloses a high-density and high-conductivity fuel cell anode, which is a technical problem to be solved at present.
Disclosure of Invention
In view of the above, the application aims to solve the technical problems that the manufacturing process is generally complex, the density of the prepared anode is low, and the conductivity does not meet the requirement in the preparation process of the anode of the fuel cell.
The first aspect of the present application provides a method for preparing an anode material for a fuel cell.
In a second aspect, the application provides an anode material for a fuel cell.
A third aspect of the application provides a fuel cell anode.
A fourth aspect of the application provides a fuel cell.
The first aspect of the present application provides a method for producing an anode material for a fuel cell, comprising: preparing a molten salt solvent, wherein the components of the molten salt solvent comprise sodium nitrate, potassium nitrate and lithium nitrate; preparing a reaction reagent, wherein the components of the reaction reagent comprise zirconium nitrate, yttrium oxide and nickel nitrate; mixing molten salt solvent and a reaction reagent on a mixer; carrying out heat preservation treatment on the mixed molten salt solvent and the reactant so as to enable the reactant to react and generate anode materials of the fuel cell; the anode material of the fuel cell is separated through the steps of centrifugation, filtration and drying.
The preparation method of the anode material of the fuel cell comprises the following steps of preparing a molten salt solvent, preparing a reaction reagent, mixing the molten salt solvent and the reaction reagent on a mixer, carrying out heat preservation treatment on the mixed molten salt solvent and the reaction reagent to enable the reaction reagent to react and generate the anode material of the fuel cell, and finally separating the anode material of the fuel cell through the steps of centrifugation, filtration and drying. Further, the components of the fused salt solvent comprise sodium nitrate, potassium nitrate and lithium nitrate, and the components of the reaction reagent comprise zirconium nitrate, yttrium oxide and nickel nitrate; during the reaction, nickel nitrate can be converted into nickel oxide, and a specific chemical reaction equation is as follows: 2Ni (NO) 3 ) 2 =4NO 2 +2NiO+O 2 Meanwhile, YSZ (yttrium stabilized zirconia) is formed, and further, nickel oxide and YSZ form anode materials, namely NiO@YSZ powder, and the NiO@YSZ powder prepared by the molten salt method is different from NiO@YSZ powder prepared by the traditional sintering method, has high compatibility with ethanol solvents, and is suitable for suspension slurry used in screen printing and spraying processes. It can be appreciated that in general, in order to load the cathode material onto the surface of the solid electrolyte, a screen printing technology is adopted, wherein an ethanol solvent solution is used for preparing a cathode material dry powder into slurry, so that screen printing is convenient, while the traditional sintering method is used for preparing LaSrCoFe powder with low matching property with an ethanol solvent, so that the screen printing effect is poor, and the conductive effect is poor.
In the technical scheme, in the components of the molten salt solvent, the molar ratio of sodium nitrate to potassium nitrate to lithium nitrate is 1-4: 1 to 5:1 to 3.
In the technical scheme, the molar ratio of sodium nitrate, potassium nitrate and lithium nitrate in the components of the molten salt solvent is 1-4: 1 to 5: 1-3, namely, in the process of preparing molten salt solvent, the mixture ratio is carried out according to mole, 1-4 parts of sodium nitrate, 1-5 parts of potassium nitrate and 1-3 parts of lithium nitrate, and further, the mole ratio of sodium nitrate, potassium nitrate and lithium nitrate is 3:2:2, controlling the mole ratio of sodium nitrate, potassium nitrate and lithium nitrate can make the reactant better dissolve in the fused salt solvent, and raise the reaction rate.
In the above technical scheme, the molar ratio of zirconium atoms, yttrium atoms and nickel atoms in the components of the reactant is 100:4: 400-800; or zirconium atom, yttrium atom and nickel atom in a molar ratio of 100:4:500, by controlling the mole ratio of zirconium atoms, yttrium atoms and nickel atoms in the reactant, the reaction can be more sufficient, and the anode has the beneficial effects of high dispersibility and high conductivity.
In the technical scheme, in the step of mixing the molten salt solvent and the reactant on the mixer, the stirring rotation speed of the mixer is more than or equal to 80r/min and less than or equal to 150r/min; for example, the stirring rotation speed of the mixer is equal to 100r/min or 120r/min, and the stirring time of the mixer is more than or equal to 2h and less than or equal to 10h; for example, the stirring time of the mixer is equal to 5 hours or 7 hours, and the mixing temperature of the mixer is equal to or higher than 90 ℃ and equal to or lower than 150 ℃, for example, the mixing temperature of the mixer is equal to 110 ℃ or 130 ℃, and the mixing speed, the stirring time and the mixing temperature of the mixer are controlled, so that each component of the reactant is uniformly mixed, the reaction rate of the later stage is improved, and the preparation efficiency is further ensured.
In the technical scheme, in the step of carrying out heat preservation treatment on the mixed molten salt solvent and the reaction reagent, the heat preservation temperature is more than or equal to 600 ℃ and less than or equal to 720 ℃; for example, the soak temperature is equal to 640 ℃ or 680 ℃; the heat preservation time is more than or equal to 5 hours and less than or equal to 8 hours, for example, the heat preservation time is equal to 6 hours or 7 hours, and the sufficient reaction of each component in the reactant can be ensured by controlling the heat preservation time and the heat preservation temperature, so that the preparation efficiency of the anode material of the fuel cell is improved.
In the above technical scheme, in the step of drying, the drying time length is greater than or equal to 1h and less than or equal to 3h. For example, the drying time is equal to 2 hours, so that the moisture in the anode material of the fuel cell can be completely removed, and the catalytic efficiency is improved.
In the technical scheme, the mass ratio of the reactant to the molten salt solvent is more than or equal to 5% and less than or equal to 60%.
According to a second aspect of the present application, there is provided an anode material for a fuel cell, where the anode material for a fuel cell is prepared according to the preparation method of the anode material for a fuel cell according to any one of the first aspect of the present application.
A third aspect of the present application provides a fuel cell anode, which is made of the anode material of the fuel cell according to the second aspect of the present application.
The fourth aspect of the present application provides a fuel cell, which includes the fuel cell anode according to the third aspect of the present application, and optionally, the fuel cell is a solid oxide fuel cell.
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 related art will be briefly described below, and it will be apparent to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic flow chart of a method for preparing an anode material of a fuel cell according to an embodiment of the present application;
fig. 2 is a schematic flow chart of a method for preparing an anode material of a fuel cell according to a second embodiment of the present application;
fig. 3 is a schematic flow chart of a method for preparing an anode material of a fuel cell according to a third embodiment of the present application;
fig. 4 is a schematic flow chart of a method for preparing an anode material of a fuel cell according to a fourth embodiment of the present application;
fig. 5 is a schematic flow chart of a method for preparing an anode material of a fuel cell according to a fifth embodiment of the present application;
fig. 6 is a schematic structural diagram of an anode of a fuel cell according to an embodiment of the present application;
fig. 7 is a schematic structural diagram of a fuel cell according to an embodiment of the present application.
The correspondence between the reference numerals and the component names in fig. 6 and 7 is:
1 fuel cell, 12 fuel cell anode, 122 fuel cell anode material.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying 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 of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
Referring to fig. 1, the present embodiment provides a method for preparing an anode material of a fuel cell, including the steps of:
s102: preparing a molten salt solvent: wherein the mass of sodium nitrate in the molten salt solvent is 100g, the mass of potassium nitrate is 100g, and the mass of lithium nitrate is 100g;
s104: preparing a reaction reagent: wherein the composition of the reactant is 0.1mol of zirconium nitrate, 0.002mol of yttrium oxide and 0.4mol of nickel nitrate;
s106: mixing molten salt solvent and a reaction reagent, and mixing on a mixer at the mixing speed of 80r/min for 2h at 90 ℃;
s108: placing the mixed materials into an alumina ceramic pot, sealing, placing the alumina ceramic pot into a muffle furnace, heating to 600 ℃, and preserving heat for 8 hours;
s110: and (5) pouring the sample obtained in the step (S108) into clean water, and centrifuging, filtering and drying to obtain the micro-nano fuel cell anode material.
Example two
Referring to fig. 2, another embodiment of the present application provides a method for preparing an anode material of a fuel cell, comprising the steps of:
s202: preparing a molten salt solvent: wherein the mass of sodium nitrate in the molten salt solvent is 400g, the mass of potassium nitrate is 500g, and the mass of lithium nitrate is 300g;
s204: preparing a reaction reagent: wherein the composition of the reactant is 0.1mol of zirconium nitrate, 0.002mol of yttrium oxide and 0.5mol of nickel nitrate;
s206: mixing molten salt solvent and a reaction reagent, and mixing on a mixer at the mixing speed of 100r/min for 5h at the mixing temperature of 110 ℃;
s208: placing the mixed materials into an alumina ceramic pot, sealing, placing the alumina ceramic pot into a muffle furnace, heating to 640 ℃, and preserving heat for 7h;
s210: and (3) pouring the sample obtained in the step (S208) into clean water, and centrifuging, filtering and drying to obtain the micro-nano fuel cell anode material.
Example III
Referring to fig. 3, the present application provides a method for preparing an anode material for a fuel cell, comprising the steps of:
s302: preparing a molten salt solvent: wherein the mass of sodium nitrate in the molten salt solvent is 200g, the mass of potassium nitrate is 300g, and the mass of lithium nitrate is 300g;
s304: preparing a reaction reagent: wherein the composition of the reactant is 0.1mol of zirconium nitrate, 0.002mol of yttrium oxide and 0.7mol of nickel nitrate;
s306: mixing molten salt solvent and a reaction reagent, and mixing on a mixer at the mixing speed of 120r/min for 7h at 130 ℃;
s308: placing the mixed materials into an alumina ceramic pot, sealing, placing the alumina ceramic pot into a muffle furnace, heating to 680 ℃, and preserving heat for 6 hours;
s310: and (3) pouring the sample obtained in the step (S308) into clean water, and obtaining the micro-nano fuel cell anode material through centrifugation, filtration and drying.
Example IV
Referring to fig. 4, the present application provides a method for preparing an anode material for a fuel cell, comprising the steps of:
s402: preparing a molten salt solvent: wherein the mass of sodium nitrate in the molten salt solvent is 200g, the mass of potassium nitrate is 200g, and the mass of lithium nitrate is 200g;
s404: preparing a reaction reagent: wherein the composition of the reactant is 0.1mol of zirconium nitrate, 0.002mol of yttrium oxide and 0.8mol of nickel nitrate;
s406: mixing molten salt solvent and a reaction reagent, and mixing on a mixer at the mixing speed of 150r/min for 10h at the mixing temperature of 150 ℃;
s408: sealing the mixed materials in an alumina ceramic pot, heating to 720 ℃ in a muffle furnace, and preserving heat for 5 hours;
s410: and (3) pouring the sample obtained in the step (S408) into clean water, and centrifuging, filtering and drying to obtain the micro-nano fuel cell anode material.
The process conditions and corresponding properties of examples one to four are shown in Table one below:
table the process conditions and corresponding properties of examples one to four
| Example 1 | Example two | Example III | Example IV | |
| Sodium nitrate: potassium nitrate: lithium nitrate (molar ratio) | 1：1：1 | 4：5：3 | 2：3：3 | 2：2：2 |
| Zirconium atom: yttrium atoms: nickel atom (molar ratio) | 100：4：400 | 100：4：500 | 100：4：700 | 100：4：800 |
| Mixing rotating speed (r/min) | 80 | 100 | 120 | 150 |
| Mixing temperature (DEG C) | 90 | 110 | 130 | 150 |
| Mixing time (h) | 2 | 5 | 7 | 10 |
| Heating temperature (DEG C) in muffle furnace | 600 | 640 | 680 | 720 |
| Heating time in muffle furnace (h) | 8 | 7 | 6 | 5 |
| Compatibility with ethanol solvent (standing suspension time, min) | 7 | 15 | 14 | 8 |
And the NiO@YSZ powder prepared by the traditional sintering method has general matching property with an ethanol solvent (standing and suspending time is 5 min).
Referring to fig. 5, the present application provides a method for preparing an anode material of a fuel cell, comprising the steps of:
s502: preparing a molten salt solvent, wherein the components of the molten salt solvent comprise sodium nitrate, potassium nitrate and lithium nitrate;
s504: preparing a reaction reagent, wherein the components of the reaction reagent comprise zirconium nitrate, yttrium oxide and nickel nitrate;
s506: mixing molten salt solvent and a reaction reagent on a mixer;
s508: carrying out heat preservation treatment on the mixed molten salt solvent and the reactant so as to enable the reactant to react and generate anode materials of the fuel cell;
s510: the anode material of the fuel cell is separated through the steps of centrifugation, filtration and drying.
The preparation method of the anode material of the fuel cell comprises the following steps of preparing a molten salt solvent, preparing a reaction reagent, mixing the molten salt solvent and the reaction reagent on a mixer, carrying out heat preservation treatment on the mixed molten salt solvent and the reaction reagent to enable the reaction reagent to react and generate the anode material of the fuel cell, and finally separating the anode material of the fuel cell through the steps of centrifugation, filtration and drying. Further, the components of the fused salt solvent comprise sodium nitrate, potassium nitrate and lithium nitrate, and the components of the reaction reagent comprise zirconium nitrate, yttrium oxide and nickel nitrate; the NiO@YSZ powder prepared by the molten salt method is different from the NiO@YSZ powder prepared by the traditional sintering method, has high matching property with an ethanol solvent, and is suitable for suspension slurry used in screen printing and spraying processes. It can be appreciated that in general, in order to load the cathode material onto the surface of the solid electrolyte, a screen printing technology is adopted, wherein an ethanol solvent solution is used for preparing a cathode material dry powder into slurry, so that screen printing is convenient, while the traditional sintering method is used for preparing LaSrCoFe powder with low matching property with an ethanol solvent, so that the screen printing effect is poor, and the conductive effect is poor.
In this example, the molar ratio of sodium nitrate, potassium nitrate and lithium nitrate in the composition of the molten salt solvent is 1 to 4:1 to 5: 1-3, namely, 1-4 parts of sodium nitrate accounting for the total mass of the molten salt solvent, 1-5 parts of potassium nitrate accounting for the total mass of the molten salt solvent, 1-3 parts of lithium nitrate accounting for the total mass of the molten salt solvent, and further, the molar ratio of sodium nitrate, potassium nitrate and lithium nitrate is 3:2:2, controlling the mole ratio of sodium nitrate, potassium nitrate and lithium nitrate can make the reactant better dissolve in the fused salt solvent, and raise the reaction rate.
In this example, the molar ratio of zirconium atoms, yttrium atoms and nickel atoms in the components of the reactant was 100:4:400 to 800, i.e. controlling the atomic ratio of zirconium atoms, yttrium atoms and nickel atoms in the components of the reactant to be 100:4:400 to 800, by controlling the atomic ratio of zirconium atoms, yttrium atoms and nickel atoms in the reactant, the anode can have the beneficial effects of high dispersibility and high conductivity. Further, the molar ratio of zirconium atoms, yttrium atoms and nickel atoms is 100:4:500,
in this embodiment, in the step of mixing the molten salt solvent and the reactive agent on the mixer, the mixing speed of the mixer is 80r/min or more and 150r/min or less; for example, the stirring rotation speed of the mixer is equal to 100r/min or 120r/min, and the stirring time of the mixer is more than or equal to 2h and less than or equal to 10h; for example, the stirring time of the mixer is equal to 5 hours or 7 hours, and the mixing temperature of the mixer is equal to or higher than 90 ℃ and equal to or lower than 150 ℃, for example, the mixing temperature of the mixer is equal to 110 ℃ or 130 ℃, and the mixing speed, the stirring time and the mixing temperature of the mixer are controlled, so that each component of the reactant is uniformly mixed, the reaction rate of the later stage is improved, and the preparation efficiency is further ensured.
In this embodiment, in the step of performing the heat-retaining treatment of the molten salt solvent and the reaction agent after mixing, the heat-retaining temperature is 600 ℃ or higher and 720 ℃ or lower; for example, the soak temperature is equal to 640 ℃ or 680 ℃; the heat preservation time is more than or equal to 5 hours and less than or equal to 8 hours, for example, the heat preservation time is equal to 6 hours or 7 hours, and the sufficient reaction of each component in the reactant can be ensured by controlling the heat preservation time and the heat preservation temperature, so that the preparation efficiency of the anode material of the fuel cell is improved.
In this embodiment, the mass ratio of the reactive agent to the molten salt solvent is 5% or more and 60% or less.
Referring to fig. 6, an embodiment of a third aspect of the present application provides a fuel cell anode 12, where the fuel cell anode 12 is made of an anode material 122 of a fuel cell according to the second aspect of the present application.
Referring to fig. 7, an embodiment of the fourth aspect of the present application provides a fuel cell 1, where the fuel cell 1 provided by the present application includes a fuel cell anode 12 according to the third aspect of the present application.
Further, the anode material of the fuel cell 1 according to the present application is an anode material prepared by the preparation method of the anode material of the fuel cell according to the first to fourth embodiments, and the electrochemical performance and stability data of the anode material obtained by the different preparation methods according to the first to fourth embodiments are shown in the following table two:
table two data of electrochemical properties and stability of anode materials obtained by different preparation methods of example one to example four
| Example 1 | Example two | Example III | Example IV | |
| Sodium nitrate: potassium nitrate: lithium nitrate (molar ratio) | 1：1：1 | 4：5：3 | 2：3：3 | 2：2：2 |
| Zirconium atom: yttrium atoms: nickel atoms | 100：4：400 | 100：4：500 | 100：4：700 | 100：4：800 |
| Mixing rotating speed (r/min) | 80 | 100 | 120 | 150 |
| Mixing temperature (DEG C) | 90 | 110 | 130 | 150 |
| Mixing time (h) | 2 | 5 | 7 | 10 |
| Heating temperature (DEG C) in muffle furnace | 600 | 640 | 680 | 720 |
| Heating time in muffle furnace (h) | 8 | 7 | 6 | 5 |
| Electrochemical Property (Rp impedance value Ω cm 2) | 0.41 | 0.15 | 0.12 | 0.35 |
| Stability (%/kilo hour) | 5.1 | 4.2 | 4.5 | 6.4 |
Whereas the electrochemical performance Rp resistance of the fuel cell prepared by the powder prepared by the conventional sintering method is about 0.5 Ω cm 2 ）。
While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any application or of what may be claimed, but rather as descriptions of features of specific embodiments of particular applications. Certain features that are described in this specification in the context of separate embodiments can also be implemented in combination in a single embodiment. On the other hand, the various features described in the individual embodiments may also be implemented separately in the various embodiments or in any suitable subcombination. Furthermore, although features may be acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.
Similarly, although operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. In some cases, multitasking and parallel processing may be advantageous. Moreover, the separation of various system modules and components in the embodiments described above should not be understood as requiring such separation in all embodiments, and it should be understood that the described program components and systems can generally be integrated together in a single software product or packaged into multiple software products.
Thus, particular embodiments of the subject matter have been described. Other embodiments are within the scope of the following claims. In some cases, the actions recited in the claims can be performed in a different order and still achieve desirable results. Furthermore, the processes depicted in the accompanying drawings are not necessarily required to be in the particular order shown, or sequential order, to achieve desirable results. In some implementations, multitasking and parallel processing may be advantageous.
It should be noted that in this document, relational terms such as "first" and "second" and the like are 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. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
The foregoing is merely exemplary of embodiments of the present application to enable those 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 (17)
1. A method for producing an anode material for a fuel cell, comprising:
preparing a molten salt solvent, wherein the components of the molten salt solvent comprise sodium nitrate, potassium nitrate and lithium nitrate;
preparing a reaction reagent, wherein the components of the reaction reagent comprise zirconium nitrate, yttrium oxide and nickel nitrate;
mixing the molten salt solvent and the reactant on a mixer;
carrying out heat preservation treatment on the mixed molten salt solvent and the reactant so as to enable the reactant to react and generate anode materials of the fuel cell;
separating out anode materials of the fuel cell through the steps of centrifugation, filtration and drying;
wherein, in the components of the molten salt solvent, the molar ratio of the sodium nitrate to the potassium nitrate to the lithium nitrate is 1-4: 1 to 5:1 to 3; in the components of the reactant, the molar ratio of the zirconium atoms in the zirconium nitrate, the yttrium atoms in the yttrium oxide and the nickel atoms in the nickel nitrate is 100:4: 400-800.
2. The method according to claim 1, wherein the molar ratio of the zirconium atom in the zirconium nitrate, the yttrium atom in the yttrium oxide, and the nickel atom in the nickel nitrate in the components of the reactant is 100:4:500.
3. the method according to claim 1, wherein in the step of mixing the molten salt solvent and the reactant on a mixer, a stirring rotation speed of the mixer is 80r/min or more and 150r/min or less.
4. A method for producing an anode material for a fuel cell according to claim 3, wherein the stirring rotation speed of the mixer is equal to 100r/min or 120r/min.
5. The method for producing an anode material for a fuel cell according to claim 1, wherein in the step of mixing the molten salt solvent and the reactive agent on a mixer, a stirring time of the mixer is 2h or more and 10h or less.
6. The method for producing an anode material for a fuel cell according to claim 5, wherein the stirring time of the mixer is equal to 5 hours or 7 hours.
7. The method for producing an anode material for a fuel cell according to claim 1, wherein in the step of mixing the molten salt solvent and the reaction reagent on a mixer, a mixing temperature of the mixer is 90 ℃ or higher and 150 ℃ or lower.
8. The method for producing an anode material for a fuel cell according to claim 7, wherein the mixing temperature of the mixer is equal to 110 ℃ or 130 ℃.
9. The method according to claim 1, wherein in the step of subjecting the molten salt solvent and the reactant after mixing to heat-retaining treatment, a heat retaining temperature is 600 ℃ or higher and 720 ℃ or lower.
10. The method according to claim 9, wherein in the step of subjecting the molten salt solvent and the reaction reagent after mixing to heat-retaining treatment, the heat-retaining temperature is equal to 640 ℃ or 680 ℃.
11. The method according to claim 1, wherein in the step of subjecting the molten salt solvent and the reactant after mixing to the heat retaining treatment, the heat retaining time is 5h or more and 8h or less.
12. The method according to claim 11, wherein in the step of subjecting the molten salt solvent and the reactant after mixing to heat-retaining treatment, the heat-retaining time is equal to 6 hours or 7 hours.
13. The method for producing an anode material for a fuel cell according to claim 1, wherein in the step of drying, a drying time period is 1h or more and 3h or less.
14. The method for producing an anode material for a fuel cell according to claim 1, wherein in the step of drying, the drying time period is equal to 2 hours.
15. An anode material of a fuel cell, characterized in that the anode material of the fuel cell is prepared according to the preparation method of an anode material of a fuel cell as claimed in any one of claims 1 to 14.
16. An anode of a fuel cell, wherein the anode of the fuel cell is prepared from the anode material of the fuel cell of claim 15.
17. A fuel cell comprising the anode of the fuel cell of claim 16.
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| KR101892909B1 (en) * | 2017-05-11 | 2018-08-29 | 한국과학기술연구원 | A method for manufacturing protonic ceramic fuel cells |
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