CN114204055A - Cathode catalyst for fuel cell and preparation method and application thereof - Google Patents
Cathode catalyst for fuel cell and preparation method and application thereof Download PDFInfo
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- CN114204055A CN114204055A CN202111506040.XA CN202111506040A CN114204055A CN 114204055 A CN114204055 A CN 114204055A CN 202111506040 A CN202111506040 A CN 202111506040A CN 114204055 A CN114204055 A CN 114204055A
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- 238000002360 preparation method Methods 0.000 title abstract description 28
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention provides a cathode catalyst for a fuel cell and a preparation method and application thereof. The cathode catalyst for the fuel cell comprises a nitrogen-doped porous carbon substrate and active particles grown on the nitrogen-doped porous carbon substrate, wherein the active particles comprise a metal cobalt inner core and cobalt oxide coated on the surface of the inner core. The invention provides a cobalt-nitrogen Co-doped porous carbon composite material C-Co-N with cobalt oxide as a shell metal cobalt as a core, which has an N-doped carbon material with a hierarchical pore structure, wherein Co-N is a carbon materialxThe catalytic sites and CoO @ Co nanoparticles with core-shell structures have synergistic effect, so that the oxygen reduction catalytic performance of the catalyst is improved, the preparation method is simple and easy to operate, and the raw materials of the carbonaceous biomass material are widely distributed, cheap and easy to obtain.
Description
Technical Field
The invention belongs to the technical field of fuel cell catalyst preparation, and relates to a cathode catalyst for a fuel cell, and a preparation method and application thereof.
Background
With the rapid development of the industrial society, the living standard of people is increasingly improved, and the environmental problems are also increasingly serious. The earth has only one, and the environmental pollution cannot be ignored. The hydrogen fuel cell is used as a clean energy converter, the raw materials are hydrogen and air, the product is water, and no substances polluting the environment are generated, so that the hydrogen fuel cell is an ideal clean energy source. The cathode catalyst material is a main limiting factor in the popularization of the hydrogen fuel cell.
Fuel cell cathode catalysts can be broadly divided into precious metal catalysts, non-precious metal catalysts, and non-metal catalysts. Currently, the noble metals Pt and Pt-based alloys are considered the most catalytically effective and most widely used fuel cell catalysts. However, the high price of the Pt leads to high production cost and scarcity of Pt resources, so that the large-scale commercial production is limited. And in the fuel cell system, a catalyst poisoning phenomenon is easily generated, and Pt also aggravates oxidation and corrosion phenomena of the carbon support during the Oxygen Reduction Reaction (ORR) until a structure collapses, thereby causing catalyst deactivation, thereby decreasing the life of the electrode. Therefore, the development of non-noble metal catalysts has great practical significance.
Non-noble metal catalysts are generally classified into the following: transition metals (mainly Fe, Co, Ni, etc.) and their oxides, sulfides and macrocyclic compounds. Non-metallic catalysts are commonly heterogeneous atom-doped carbon materials such as N, S, P, B. Especially, N-doped carbon material, since N atom has stronger electronegativity than C atom, resulting in non-uniform charge distribution in the carbon matrix, adjacent carbon atoms will become active sites for oxygen adsorption and reduction, thereby improving the catalytic activity of ORR.
The porous carbon material has the unique performances of high surface area, high porosity, high stability, high mechanical strength, higher conductivity and the like, and is an excellent carrier material.
CN102451727A discloses an M/N-C catalyst and its preparation and application, wherein cobalt salt and polypyrrole (PPy) are directly impregnated, so that after Co and N on PPy act to form a catalytic center, the sample is directly subjected to high-temperature heat treatment to cause PPy to be thermally decomposed to form a carbon skeleton, and the carbon skeleton is directly used as a carbon carrier of a novel catalyst to enhance the conductivity of the catalyst. Although polypyrrole can provide larger specific surface area for the catalytic particles Fe, Co and Ni after carbonization, the preparation process of the method is complicated and has a plurality of influence factors, the polypyrrole carbonization process needs high-temperature treatment and needs protection of inert gas to prevent the catalytic particles from being oxidized, and the activity of the catalyst cannot meet the practical application requirements of the fuel cell.
CN102916203A discloses a proton exchange membrane fuel cell cathode non-platinum catalyst and a preparation method thereof, which comprises the steps of preparing melamine formaldehyde resin, adding metal salt, carrying out complex reaction between the melamine formaldehyde resin and the metal salt to form a complex, evaporating a solvent, and carrying out thermal treatment decomposition to obtain the proton exchange membrane fuel cell cathode non-platinum catalyst with a hollow spherical structure. However, the melamine formaldehyde resin has poor conductivity, so that the conductivity of the catalyst is reduced, and similar to the scheme, the preparation of the hollow spherical structure can not avoid high-temperature heat treatment on organic matters, and the generation of harmful gases with complex components, which is generated therewith, is not favorable for meeting the requirements of energy conservation and environmental protection.
Therefore, how to obtain a fuel cell cathode oxygen reduction reaction catalyst with excellent catalytic activity by using cheap and easily available raw materials and using a simple and easy-to-operate preparation method is an urgent technical problem to be solved.
Disclosure of Invention
The invention aims to provide a cathode catalyst for a fuel cell, and a preparation method and application thereof. The invention provides a cobalt-nitrogen Co-doped porous carbon composite material C-Co-N with cobalt oxide as a shell metal cobalt as a core, which has an N-doped carbon material with a hierarchical pore structure to form Co-NxThe catalytic sites and CoO @ Co nanoparticles with core-shell structures have synergistic effects, so that the oxygen reduction catalytic performance of the catalyst is improved, the preparation method is simple and easy to operate, and the carbonaceous biomass raw materials are widely distributed, cheap and easy to obtain.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a cathode catalyst for a fuel cell, including a nitrogen-doped porous carbon substrate and active particles grown on the nitrogen-doped porous carbon substrate, where the active particles include a metallic cobalt core and cobalt oxide coated on a surface of the core.
The invention provides a cobalt-nitrogen Co-doped porous carbon composite material C-Co-N with cobalt oxide as a shell metal cobalt as a core, which has an N-doped carbon material with a hierarchical pore structure to form Co-NxThe catalytic sites and CoO @ Co nanoparticles with core-shell structures simultaneously improve the oxygen reduction catalytic performance of the catalyst through synergistic effect.
In the invention, the porous carbon substrate is doped with N, and the electronegativity of N atoms is stronger than that of C atoms, so that the charge distribution in the carbon substrate is uneven, and adjacent carbon atoms become active sites for oxygen adsorption and reduction, thereby improving the catalytic activity of ORR. If nitrogen doping is not performed, the catalytic activity of the catalyst with respect to ORR is affected.
Preferably, the raw material of the cathode catalyst for a fuel cell includes carbonaceous biomass, a cobalt salt, and a nitrogen source.
According to the invention, the carbonaceous biomass is selected as the raw material, the distribution is wide, the raw material is cheap and easy to obtain, and the biomass waste is preferably selected, so that the waste is changed into valuable, various biological wastes can be well treated, the carbon resource in the nature is fully utilized, the production cost of the carbon material is reduced, and the sustainable development is promoted.
Preferably, the nitrogen-doped porous carbon substrate further comprises elemental silicon.
In the invention, aiming at different types of carbon-containing biomass, the catalyst also comprises silicon element, and the silicon element is also beneficial to establishing active sites of the oxygen reduction catalyst.
Preferably, the percentage by mass of the element C is 80 to 85%, for example, 80%, 81%, 82%, 83%, 84%, 85% or the like, based on 100% by mass of the cathode catalyst for a fuel cell.
Preferably, the percentage of the O element by mass is 6 to 15%, for example, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or the like, based on 100% by mass of the cathode catalyst for a fuel cell.
Preferably, the mass ratio of the N element is 3 to 6%, for example, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, or 6% based on 100% by mass of the cathode catalyst for a fuel cell.
Preferably, the mass ratio of the Si element is 1 to 4%, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, or 4% based on 100% by mass of the cathode catalyst for a fuel cell.
Preferably, the mass ratio of the Co element is 1 to 3%, for example, 1%, 1.5%, 2%, 2.5%, or 3% based on 100% by mass of the cathode catalyst for a fuel cell.
In the invention, the mass ratio of each element in the catalyst is synergistic, so that excellent oxygen reduction catalytic activity is realized together.
In a second aspect, the present invention provides a method for producing a cathode catalyst for a fuel cell according to the first aspect, the method comprising the steps of:
(1) mixing carbonaceous biomass, cobalt salt and a regulator to obtain an alkaline mixed solution, and carrying out hydrothermal treatment and freeze drying to obtain a precursor;
(2) and (2) carrying out carbonization heat treatment on the precursor in the step (1) under a protective atmosphere to obtain the cathode catalyst for the fuel cell.
According to the invention, carbon-containing biomass with wide sources is used as a raw material to prepare the oxygen reduction catalyst with excellent catalytic performance, the carbon-rich biomass material is subjected to hydrothermal treatment by using cobalt salt, and then is subjected to carbonization to obtain a nitrogen-doped porous carbon substrate and active particles growing on the nitrogen-doped porous carbon substrate, wherein the active particles comprise a metal cobalt inner core and cobalt oxide coating the surface of the inner core.
According to the invention, through hydrothermal treatment of cobalt salt and biomass materials in a weakly alkaline solution, due to the action of oxygen-containing functional groups in the biomass and subsequent nitrogen doping and carbonization processes (when the carbonaceous biomass contains nitrogen elements, nitrogen doping is not needed), the obtained active particles can be presented in a mode that an inner core is metal cobalt and an outer layer is coated with cobalt oxide, and the synergistic effect of hydrothermal treatment and subsequent nitrogen doping realizes the presentation of cobalt-nitrogen catalytic active sites and the synergistic effect of nitrogen-doped porous carbon materials, Co-Nx catalytic sites and CoO @ Co nanoparticles with a core-shell structure, so that the excellent oxygen reduction catalytic performance of the catalyst material is achieved.
According to the invention, the carbonaceous biomass is selected as a raw material, is widely distributed, is cheap and easy to obtain, and is preferably a biomass waste material, so that waste is changed into valuable, various biological wastes can be well treated, carbon resources in the nature are fully utilized, the production cost of the carbon material is reduced, the sustainable development is promoted, and the carbonaceous biomass contains oxygen-containing functional groups, so that the production of a CoO @ Co core-shell structure can be favorably realized.
In the present invention, the mixed solution in step (1) is weakly alkaline, so that the formation of Co-containing nanoparticles can be more easily achieved, and if the mixed solution is non-alkaline, the formation of Co particles is difficult.
In the present invention, the carbonaceous biomass includes, but is not limited to anaphalis yedoensis, typha orientalis or phoenix tree wadding or soybean curd residue, etc.
Preferably, the cobalt salt of step (1) comprises cobalt acetate.
Preferably, the conditioning agent in step (1) comprises ammonia.
In the invention, ammonia water is selected as a regulator, which is more beneficial to the formation of Co-containing nano particles.
Preferably, the pH value of the alkaline mixed solution in the step (1) is 8-10, such as 8, 8.5, 9, 9.5 or 10.
In the invention, the porous carbon material has an overlarge pore structure and a damaged multi-level pore structure due to overlarge pH value, and the Co-containing nanoparticles are not easily formed due to the overlarge pH value.
Preferably, the temperature of the hydrothermal reaction in step (1) is 180 to 200 ℃, for example 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃.
Preferably, the hydrothermal reaction time in the step (1) is 10-14 h, such as 10h, 11h, 12h, 13h or 14 h.
In the invention, the hydrothermal time is too short, which is not beneficial to the formation of Co particles, and the hydrothermal time is too long, which can cause the growth of Co particles to be too large.
Preferably, the freeze-drying time in step (1) is at least 24h, such as 24h, 28h, 30h or 35 h.
Preferably, in step (2), a nitrogen source is added to mix with the precursor in step (1).
In the invention, when the carbon-containing biomass does not contain nitrogen elements, nitrogen doping operation is required.
Preferably, the nitrogen source comprises melamine.
Preferably, the temperature of the carbonization heat treatment in the step (2) is 700 to 900 ℃, for example 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃.
Preferably, the time of the carbonization heat treatment in the step (2) is 2 to 3 hours, such as 2 hours or 3 hours.
Preferably, the carbonized heat treated material in the step (2) is washed with water and settled.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing carbonaceous biomass, cobalt salt and ammonia water to obtain an alkaline mixed solution with the pH value of 8-10, carrying out hydrothermal treatment at 180-200 ℃ for 10-14 h, and carrying out freeze drying for at least 24h to obtain a precursor;
(2) and (2) mixing the precursor obtained in the step (1) with a nitrogen source under a protective atmosphere, carrying out carbonization heat treatment for 2-3 h at 700-900 ℃, washing with water, and settling to obtain the cathode catalyst for the fuel cell.
In a third aspect, the present invention also provides a fuel cell including the cathode catalyst for a fuel cell according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a cobalt-nitrogen Co-doped porous carbon composite material C-Co-N with cobalt oxide as a shell metal cobalt as a core, which has an N-doped carbon material with a hierarchical pore structure to form Co-NxCatalytic sites simultaneously with core-shell structureThe CoO @ Co nano particles improve the oxygen reduction catalytic performance of the catalyst through synergistic effect, the preparation method is simple and easy to operate, and the carbonaceous biomass material is wide in raw material distribution, low in price and easy to obtain. The half-wave potential of the cathode catalyst for the fuel cell provided by the invention can reach more than 0.801V, the time and the pH value of hydrothermal reaction are further regulated, and the half-wave potential can reach more than 0.835V.
Drawings
Fig. 1 is an XRD pattern of the cathode catalyst for a fuel cell provided in example 1.
Fig. 2 is an SEM image of the cathode catalyst for a fuel cell provided in example 1.
Fig. 3 is a TEM image of the cathode catalyst for a fuel cell provided in example 1.
Fig. 4 is an XPS chart of the cathode catalyst for a fuel cell provided in example 1.
Fig. 5 is an XPS chart of the cathode catalyst for a fuel cell provided in example 1.
Fig. 6 is an XPS chart of the cathode catalyst for a fuel cell provided in example 1.
Fig. 7 is a graph comparing electrochemical performances of the cathode catalysts for fuel cells provided in example 1 and comparative example 4.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a cathode catalyst for a fuel cell, which includes a nitrogen-doped porous carbon substrate and active particles grown on the nitrogen-doped porous carbon substrate, wherein the active particles include a metallic cobalt core and cobalt oxide coated on the surface of the core.
The preparation method of the catalyst comprises the following steps:
(1) washing typha angustifolia flower spikes with deionized water, naturally airing, bursting, shearing, weighing 0.9g of typha angustifolia flower spikes, adding 0.1g of cobalt acetate into 30ml of deionized water to prepare a solution, putting the solution into a beaker b, pouring the typha angustifolia flower spikes sheared in the beaker a into the solution in the beaker b, fully stirring and infiltrating, then dropwise adding 5ml of ammonia water to adjust the pH value to 9, stirring uniformly, quickly pouring into a hydrothermal kettle with the capacity of 40ml, putting into an oven, heating to 180 ℃ for hydrothermal for 12 hours, pouring out a mixture after cooling to room temperature, extruding liquid, only retaining solid, and freeze-drying for 24 hours to obtain a precursor;
(2) taking a clean crucible, adding 0.4g of melamine at the bottom, weighing 0.6g of freeze-dried precursor (black brown solid) and placing the precursor on the upper part of the crucible, then performing carbonization heat treatment at 800 ℃ in a vacuum furnace for 2h by taking nitrogen as protective gas, cooling to room temperature to obtain black fluffy solid, grinding the black fluffy solid into black powder, cleaning the black fluffy solid with deionized water, and settling to obtain the catalyst material taking cobalt oxide growing on a nitrogen-doped porous carbon substrate as a shell and taking metal cobalt as a core.
Fig. 1 shows an XRD pattern of the cathode catalyst for a fuel cell provided in example 1, and as can be seen from fig. 1, the prepared material includes an amorphous carbon substrate, Co and CoO.
Fig. 2 shows an SEM image of the cathode catalyst for a fuel cell provided in example 1, and fig. 3 shows a TEM image of the cathode catalyst for a fuel cell provided in example 1, and it can be seen from fig. 2 that the prepared material is a multi-stage porous carbon material substrate, and the morphology of Co particles are uniformly grown and distributed, and it can be seen from fig. 3 that the Co particles are CoO @ Co nanoparticles with a core-shell structure.
Fig. 4, 5 and 6 show XPS diagrams of the cathode catalyst for a fuel cell provided in example 1, and it can be seen from fig. 4 that the prepared material mainly contains five elements of C, N, O, Si and Co, in respective proportions of C (84%), O (9%), N (3%), Si (2%) and Co (2%). Five peaks corresponding to pyridine-N (398.3eV), Co-N (399.7eV), pyrrole-N (401.2eV), graphite-N (402.6eV), and N oxide (404.7eV) were observed from the high-resolution spectrum of N1s in FIG. 5. The existence of Co-N bond indicates the combination of Co and N, thereby forming Co-Nx catalytic active sites and improving the catalytic activity of the catalyst. The pyridine-N can effectively improve the initial potential of the ORR catalyst and the wettability of the material, and the graphite-N can greatly improve the limiting current density of the ORR catalyst. From fig. 6, the peaks of Co and Co2+ in the zero valence state can be seen, illustrating the presence of metallic cobalt and cobalt oxide.
Example 2
The present embodiment provides a cathode catalyst for a fuel cell, which includes a nitrogen-doped porous carbon substrate and active particles grown on the nitrogen-doped porous carbon substrate, wherein the active particles include a metallic cobalt core and cobalt oxide coated on the surface of the core.
The preparation method of the catalyst comprises the following steps:
(1)0.1g of cobalt acetate is added with 30ml of deionized water to prepare a solution, then 1g of bean curd residue is weighed and poured into the solution in a beaker for multiple times, the solution is fully stirred and soaked, then 5ml of ammonia water is dripped to adjust the pH value to 10, the mixture is quickly poured into a hydrothermal kettle with the capacity of 40ml after being uniformly stirred, the hydrothermal kettle is put into an oven and heated to 200 ℃ for 10 hours, the mixture is poured out after being cooled to the room temperature, liquid is squeezed out, only solid is left, and the mixture is frozen and dried for 30 hours to obtain a precursor;
(2) taking a clean crucible, weighing 0.5g of freeze-dried dark brown solid, placing the dark brown solid at the bottom of the crucible, then taking nitrogen as protective gas, carrying out carbonization heat treatment at 900 ℃ in a vacuum furnace for 2h, cooling to room temperature to obtain black fluffy solid, grinding the black fluffy solid into black powder, cleaning the black fluffy solid with deionized water, and settling to obtain the catalyst material taking cobalt oxide growing on a nitrogen-doped porous carbon substrate as a shell metal cobalt as a core. Because the biomass is rich in N element, further nitrogen doping treatment is not needed.
Example 3
The present embodiment provides a cathode catalyst for a fuel cell, which includes a nitrogen-doped porous carbon substrate and active particles grown on the nitrogen-doped porous carbon substrate, wherein the active particles include a metallic cobalt core and cobalt oxide coated on the surface of the core.
The preparation method of the catalyst comprises the following steps:
(1) cleaning the silvergrass with deionized water, shearing, naturally drying, weighing 0.9g of the silvergrass, putting the weighed silvergrass into a beaker a, adding 30ml of deionized water into 0.1g of cobalt acetate to prepare a solution, putting the solution into a beaker b, pouring the silvergrass sheared from the beaker a into the solution in the beaker b, fully stirring and infiltrating, then dropwise adding 5ml of ammonia water to adjust the pH value to 8, quickly pouring the solution into a hydrothermal kettle with the capacity of 40ml after stirring uniformly, putting the kettle into an oven, heating to 180 ℃, preserving heat for 12 hours, pouring out the mixture after cooling to room temperature, squeezing out liquid, only retaining solid, and freeze-drying for 35 hours to obtain a precursor;
(2) taking a clean crucible, adding 0.36g of melamine at the bottom, weighing 0.58g of freeze-dried dark brown solid, placing the dark brown solid on the upper part of the crucible, then carrying out carbonization heat treatment at 800 ℃ in a vacuum furnace for 2h by taking nitrogen as protective gas, cooling to room temperature to obtain black fluffy solid, grinding the black fluffy solid into black powder, cleaning the black fluffy solid with deionized water, and settling to obtain the catalyst material taking cobalt oxide growing on a nitrogen-doped porous carbon substrate as a shell and taking metal cobalt as a core.
Example 4
The present embodiment provides a cathode catalyst for a fuel cell, which includes a nitrogen-doped porous carbon substrate and active particles grown on the nitrogen-doped porous carbon substrate, wherein the active particles include a metallic cobalt core and cobalt oxide coated on the surface of the core.
The preparation method of the catalyst comprises the following steps:
(1) cleaning the silvergrass with deionized water, shearing, naturally drying, weighing 0.9g of the silvergrass, putting the weighed silvergrass into a beaker a, adding 30ml of deionized water into 0.2g of cobalt acetate to prepare a solution, putting the solution into a beaker b, pouring the silvergrass sheared from the beaker a into the solution in the beaker b, fully stirring and infiltrating, then dropwise adding 5ml of ammonia water to adjust the pH value to 8, quickly pouring the solution into a hydrothermal kettle with the capacity of 40ml after stirring uniformly, putting the kettle into an oven, heating to 180 ℃, preserving heat for 12 hours, pouring the mixture after cooling to room temperature, squeezing out liquid, only preserving solid, and freeze-drying for 24 hours;
(2) taking a clean crucible, adding 0.36g of melamine at the bottom, weighing 0.58g of freeze-dried dark brown solid, placing the dark brown solid on the upper part of the crucible, then carrying out carbonization heat treatment at 800 ℃ in a vacuum furnace for 2h by taking nitrogen as protective gas, cooling to room temperature to obtain black fluffy solid, grinding the black fluffy solid into black powder, cleaning the black fluffy solid with deionized water, and settling to obtain the catalyst material taking cobalt oxide growing on a nitrogen-doped porous carbon substrate as a shell and taking metal cobalt as a core.
Example 5
The difference between this example and example 1 is that the hydrothermal time in step (1) of this example is 8 h.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
The difference between this example and example 1 is that the hydrothermal time in step (1) of this example is 15 h.
The remaining preparation methods and parameters were in accordance with example 1.
Example 7
The difference between this example and example 1 is that the pH value in step (1) of this example is 12.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The difference between the comparative example and the example 1 is that no ammonia water regulator is added in the step (1) of the comparative example.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 2
The present comparative example differs from example 1 in that ordinary oven drying is used in step (1) of the present comparative example, and freeze drying is not used.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 3
The comparative example differs from example 1 in that no melamine was added in step (2) of the comparative example and argon was used as the shielding gas.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 4
This comparative example provides a cathode catalyst for a fuel cell, which is a commercial Pt/C catalyst.
Fig. 7 is a graph showing electrochemical properties of the cathode catalysts for fuel cells provided in example 1 and comparative example 4, and it can be seen from fig. 7 that the catalysts prepared by the method of example 1 have comparable catalytic oxygen reduction performance to the conventional Pt/C catalyst.
Table 1 shows the elemental compositions and contents of the cathode catalysts for fuel cells provided in examples 1 to 7.
TABLE 1
| C(％) | O(％) | N(％) | Co(％) | Si(％) | |
| Example 1 | 84 | 9 | 3 | 2 | 2 |
| Example 2 | 85 | 8 | 4 | 2 | 1 |
| Example 3 | 85 | 8 | 3 | 2 | 2 |
| Example 4 | 83 | 9 | 3 | 3 | 2 |
| Example 5 | 83 | 10 | 4 | 1 | 2 |
| Example 6 | 80 | 11 | 4 | 4 | 1 |
| Example 7 | 80 | 12 | 3 | 4 | 1 |
Electrochemical performance tests were performed on the cathode catalysts for fuel cells provided in examples 1 to 7 and comparative examples 1 to 4 under the following test conditions:
1) the preparation concentration is 0.1 mol.L-1The KOH solution is sealed and placed in a dark place, and high-purity oxygen needs to be introduced into the solution before electrochemical testing is carried out;
2) the electrochemical workstation is CHI760e (Shanghai Chenghua apparatus Co., Ltd.), and in a three-electrode system, graphite is used as a counter electrode, a mercury/mercury oxide electrode (Hg/HgO) is used as a reference electrode, a core-shell structure is doped with a porous carbon material and directly used as a working electrode, and the concentration of the doped porous carbon material is 0.1 mol.L-1The ORR (non-noble metal redox) electrochemical performance of the KOH electrolyte is tested by adopting a Linear Sweep Voltammetry (LSV), the ORR half-wave potential E1/2(vs. RHE) is obtained through the test, and the result is shown in Table 2.
TABLE 2
| Half-wave potential (V) | |
| Example 1 | 0.847 |
| Example 2 | 0.843 |
| Example 3 | 0.848 |
| Example 4 | 0.835 |
| Example 5 | 0.803 |
| Example 6 | 0.81 |
| Example 7 | 0.801 |
| Comparative example 1 | 0.798 |
| Comparative example 2 | 0.786 |
| Comparative example 3 | 0.769 |
| Comparative example 4 | 0.823 |
The catalytic performance of the catalyst can be judged according to the half-wave potential in the table 1, and the larger the initial potential is, the larger the limiting current density is, the larger the half-wave potential is, and the better the performance of the catalyst is.
From the data results of example 1 and examples 5 and 6, it can be seen that too short hydrothermal time is not favorable for the formation of Co particles at catalytic sites, and too long hydrothermal time can result in too large Co particle growth. Both of these cases do not contribute to the improvement of catalytic activity of the catalyst for oxygen reduction.
From the data results of example 1 and example 7, it is known that an excessive pH value in step (1) results in an excessive pore structure of the porous carbon material, which results in a destruction of the hierarchical pore structure and a decrease in the specific surface area of the material.
From the data results of example 1 and comparative example 1, it can be seen that the addition of ammonia water regulator results in too low a pH value, which is not favorable for the formation of Co-containing nanoparticle active sites.
From the data results of example 1 and comparative example 2, it can be seen that the absence of freeze-drying is not conducive to the formation and maintenance of a hierarchical pore structure and to the exposure of catalytic sites.
From the data results of example 1 and comparative example 3, it is understood that the formation of nitrogen-doped carbon active sites and Co — N cannot be achieved without nitrogen dopingxFormation of active sites.
From the data results of the example 1 and the comparative example 4, it can be known that compared with the conventional Pt/C catalyst, the catalyst provided by the invention has the advantages of comparable catalytic oxygen reduction performance, cheap and easily available raw materials, simple preparation method and difficult occurrence of catalyst poisoning.
In summary, the invention provides a cobalt-nitrogen Co-doped porous carbon composite material C-Co-N with cobalt oxide as a shell metal cobalt as a core, and the porous carbon composite material C-Co-N has an N-doped carbon material with a hierarchical pore structure to form Co-NxThe catalytic sites and CoO @ Co nanoparticles with core-shell structures have synergistic effect, so that the oxygen reduction catalytic performance of the catalyst is improved, the preparation method is simple and easy to operate, and the raw materials of the carbonaceous biomass material are widely distributed, cheap and easy to obtain. The half-wave potential of the cathode catalyst for the fuel cell provided by the invention can reach more than 0.801V, the time and the pH value of hydrothermal reaction are further regulated, and the half-wave potential can reach more than 0.835V.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The cathode catalyst for the fuel cell is characterized by comprising a nitrogen-doped porous carbon substrate and active particles grown on the nitrogen-doped porous carbon substrate, wherein the active particles comprise a metal cobalt inner core and cobalt oxide coated on the surface of the inner core.
2. The cathode catalyst for a fuel cell according to claim 1, wherein the raw material of the cathode catalyst for a fuel cell includes carbonaceous biomass, a cobalt salt, and a nitrogen source.
3. The cathode catalyst for a fuel cell according to claim 1 or 2, wherein the nitrogen-doped porous carbon substrate further comprises elemental silicon;
preferably, the mass percentage of the element C is 80-85% based on 100% of the mass of the cathode catalyst for the fuel cell;
preferably, the mass percentage of the O element is 6-15% based on 100% of the mass of the cathode catalyst for the fuel cell;
preferably, the mass percentage of the N element is 3-6% based on 100% of the mass of the cathode catalyst for the fuel cell;
preferably, the mass ratio of the Si element is 1-4% based on 100% of the mass of the cathode catalyst for the fuel cell;
preferably, the mass ratio of the Co element is 1 to 3% based on 100% by mass of the cathode catalyst for a fuel cell.
4. A method for preparing a cathode catalyst for a fuel cell according to any one of claims 1 to 3, comprising the steps of:
(1) mixing carbonaceous biomass, cobalt salt and a regulator to obtain an alkaline mixed solution, and carrying out hydrothermal treatment and freeze drying to obtain a precursor;
(2) and (2) carrying out carbonization heat treatment on the precursor in the step (1) under a protective atmosphere to obtain the cathode catalyst for the fuel cell.
5. The method of preparing a cathode catalyst for a fuel cell according to claim 4, wherein the cobalt salt of step (1) comprises cobalt acetate;
preferably, the conditioning agent in step (1) comprises ammonia.
6. The method for preparing a cathode catalyst for a fuel cell according to claim 4 or 5, wherein the pH of the alkaline mixed solution in the step (1) is 8 to 10;
preferably, the temperature of the hydrothermal reaction in the step (1) is 180-200 ℃;
preferably, the hydrothermal reaction time in the step (1) is 10-14 h;
preferably, the freeze-drying time of step (1) is at least 24 h.
7. The method for preparing a cathode catalyst for a fuel cell according to any one of claims 4 to 6, wherein in the step (2), a nitrogen source is added to be mixed with the precursor in the step (1);
preferably, the nitrogen source comprises melamine;
preferably, the temperature of the carbonization heat treatment in the step (2) is 700-900 ℃;
preferably, the time of the carbonization heat treatment in the step (2) is 2-3 h.
8. The method for preparing a cathode catalyst for a fuel cell according to any one of claims 4 to 7, wherein the carbonized heat-treated material of step (2) is sequentially subjected to water washing and sedimentation.
9. The method for preparing a catalyst according to any one of claims 4 to 8, characterized in that it comprises the following steps:
(1) mixing carbonaceous biomass, cobalt salt and ammonia water to obtain an alkaline mixed solution with the pH value of 8-10, carrying out hydrothermal treatment at 180-200 ℃ for 10-14 h, and carrying out freeze drying for at least 24h to obtain a precursor;
(2) and (2) mixing the precursor obtained in the step (1) with a nitrogen source under a protective atmosphere, carrying out carbonization heat treatment for 2-3 h at 700-900 ℃, washing with water, and settling to obtain the cathode catalyst for the fuel cell.
10. A fuel cell characterized by comprising the cathode catalyst for a fuel cell according to any one of claims 1 to 3.
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