CN109346695B - Nickel-based material with spherical core-nano porous shell composite structure and preparation method thereof - Google Patents
Nickel-based material with spherical core-nano porous shell composite structure and preparation method thereof Download PDFInfo
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- CN109346695B CN109346695B CN201811181183.6A CN201811181183A CN109346695B CN 109346695 B CN109346695 B CN 109346695B CN 201811181183 A CN201811181183 A CN 201811181183A CN 109346695 B CN109346695 B CN 109346695B
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- H—ELECTRICITY
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- 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
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
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- H01M4/90—Selection of catalytic material
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- 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 invention discloses a nickel-based material with a spherical core-nano porous shell composite structure and a preparation method thereof. The method comprises the following steps: (1) dissolving nickel acetate in deionized water to prepare a nickel acetate solution, then adding PVP, and stirring for dissolving; (2) stirring and mixing the solution obtained in the step (1) and an oxalic acid solution, adjusting the pH value of the mixture to 7.0-8.5, and standing and culturing the mixture for 0.5-12 h at the temperature of 20-60 ℃ after stirring; (3) and filtering and collecting precipitates, cleaning for 3-5 times, drying at 70-95 ℃ for 6-12 hours, performing heat treatment at 320-400 ℃ for 15-60 min under the protection of protective gas, and cooling to room temperature to obtain the catalyst. The bell-shaped composite core-shell structure can effectively perform embedded type composite of the core-shell structure and the nano-porous structure, realizes the composite embedding of the spherical nickel core and the nano-porous nickel shell, has larger space between the core shells and shows the bell structure.
Description
Technical Field
The invention belongs to the field of nickel-based materials with a spherical core-nano porous shell composite structure and a preparation method thereof.
Background
The nickel-based nano material with the core-shell structure and the nano porous structure is an important functional material, and is widely applied to the fields of electrocatalysis, chemical catalysis, electrode materials and the like based on the inherent chemical reaction activity.
With the development of the new energy technology revolution in the international society, the research and application of lithium batteries and fuel batteries are pushed to the historical sharp air ports, the most important key part of the batteries, namely electrodes, is the bottleneck of the development of high-energy density batteries, the effective electrode materials at present mainly comprise noble metals such as Pt, Ir, Ru and the like, and the noble metals are expensive and limited in quantity, so that the price of the electrode materials is high, and the application and popularization of the fuels and the lithium batteries are limited. In the long-term research process, the nickel nano material is found to have the characteristics of low cost, high corrosion resistance and high catalytic activity, so that the internal organization structure is improved, the catalytic performance is improved, and the nickel nano material can effectively replace or compound a noble metal material to manufacture an effective active electrode material and is the most promising active electrode material.
Research on improving the catalytic performance of the nickel electrode shows that the nickel electrode can be realized by changing the microstructure of a nickel catalyst, namely, a nano porous nickel material is adopted, and the nano porous structure has excellent physicochemical properties such as large porosity, low density, large specific surface area, high chemical reaction activity and the like. The preparation method can use electrochemical deposition technology (or template-assisted electrodeposition technology), dealloying technology and powder molding sintering technology. The porous material prepared by the technology is only a nano nickel material with a single porous structure. Another core-shell structured nano nickel material can be used, and the core-shell structured nano nickel-based material has a multi-layer surface, thereby showing special physical properties such as shape, size, surface area and the like. The preparation method comprises an electrochemical deposition technology, a wet chemical reduction technology, a hydrothermal reaction technology and the like. The core-shell structure prepared by the technology is only a single core-shell structure nano nickel material. The two technical processes can not prepare the metal nickel microsphere material with the core-porous shell structure composite structure either by preparing the nickel nano material with the single porous structure or by preparing the nickel nano material with the single core-shell structure.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nickel-based material with a spherical core-nano porous shell composite structure and a preparation method thereof, which can solve the problem that the spherical core-porous shell composite structure is difficult to prepare in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a nickel-based material with a spherical core-nano porous shell composite structure comprises the following steps:
(1) dissolving nickel acetate in deionized water to prepare a nickel acetate solution with the molar concentration of 0.01-0.10 mole/L, then adding PVP, and stirring to dissolve; wherein, the weight of PVP is 0.5-2% of the weight of nickel acetate;
(2) mixing and stirring the solution obtained in the step (1) and an oxalic acid solution with the molar concentration of 0.011-0.11 mole/L, adjusting the pH value of the mixture to 7.0-8.5, and standing and culturing for 0.5-12 hours at the temperature of 20-60 ℃ after stirring; wherein the volume ratio of the oxalic acid solution to the solution obtained in the step (1) is 0.5-1.5: 0.5-1.0;
(3) filtering and collecting precipitates, cleaning for 3-5 times, drying at 70-95 ℃ for 6-12 hours, carrying out heat treatment at 320-400 ℃ for 15-60 min under the protection of protective gas, and cooling to room temperature to obtain the catalyst.
Further, the molar concentration of the nickel acetate solution in the step (1) is 0.05 mole/L.
Further, the weight of PVP in step (1) was 1.2% of the weight of nickel acetate.
Further, the volume ratio of the solution of the Chinese herbal acid in the step (2) to the solution obtained in the step (1) is 1: 1.
Further, the molar concentration of the solution of the Chinese herbal acid in the step (2) is 0.055 mole/L.
Further, the culture conditions in the step (2) are as follows: adjusting the pH value to 8.0, and performing static culture for 0.5h at the temperature of 40 ℃.
Further, the heat treatment process in the step (3) is as follows:
and (3) putting the dried precipitate into a quartz boat, putting the quartz boat into the middle position where a tubular atmosphere furnace thermocouple is positioned, filling the quartz boat with argon or hydrogen as protective gas, and then carrying out heat treatment for 15-60 min at 320-400 ℃.
Further, the cleaning process in the step (3) is as follows:
washing with deionized water for 3-5 times, and finally washing with absolute ethyl alcohol.
The nickel-based material with the spherical core-nano porous shell composite structure is prepared by the method.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a nickel-based material with a spherical core-nano porous shell composite structure, which is characterized in that nickel oxalate microspheres with a spherical core-spherical radial shell structure are synthesized by controlling, and the core-shell structure and the porous structure can be effectively prepared by compounding by controlling the heat treatment process conditions, so that the spherical nickel core and the nano porous nickel shell are effectively nested, and a large space is formed between the nickel core and the nickel shell to form a bell-shaped core-shell nano porous structure.
2. The invention can effectively compound the core-shell structure and the porous structure, realizes the compound nesting of the spherical nickel core and the nano porous nickel shell, and has larger space between the core and the shell, and the metal nickel microsphere with the core-porous shell structure has two structures of the core-shell structure and the porous structure.
Drawings
FIG. 1 is a drawing of a nickel oxalate microsphere with a spherical radial shell structure;
fig. 2 is a picture of nickel oxalate microspheres having a spherical core-spherical radial shell structure;
FIG. 3 is a picture of a nickel-based microsphere having a spherical core-nanoporous shell composite structure;
fig. 4 is a picture of a nanoporous shell structure of a nickel-based microsphere.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate the understanding of the present invention by those skilled in the art, but it should be understood that the present invention is not limited to the scope of the embodiments, and it will be apparent to those skilled in the art that various changes may be made without departing from the spirit and scope of the invention as defined and defined in the appended claims, and all matters produced by the invention using the inventive concept are protected.
Example 1
A preparation method of a nickel-based material with a spherical core-nano porous shell composite structure comprises the following steps:
(1) adding nickel acetate into deionized water, stirring and dissolving to prepare a nickel acetate solution with the molar concentration of 0.01mole/L, then adding PVP with the weight of 0.5% of that of the nickel acetate into the nickel acetate solution, and stirring and dissolving to obtain a mixed solution for later use;
(2) adding oxalic acid into deionized water, stirring and dissolving to prepare an oxalic acid solution with the molar concentration of 0.011 mole/L;
(3) mixing the mixed solution obtained in the step (1) with an oxalic acid solution according to the volume ratio of 0.5:1.0, uniformly stirring, quickly dropwise adding ammonia water, adjusting the pH value to 7.0, stirring again, and then standing and culturing at 20 ℃ for 12 hours;
(4) after the standing culture is finished, filtering, collecting precipitates, washing the precipitates for multiple times by using deionized water, washing the precipitates once by using absolute ethyl alcohol, and then placing the precipitates in a drying oven at 70 ℃ for drying for 12 hours;
(5) and placing the dried product in a quartz boat, then placing the quartz boat in the middle position of a thermocouple in a tubular atmosphere furnace, filling argon as protective gas into the quartz boat, then carrying out heat treatment for 60min at 320 ℃, cooling to room temperature to obtain the nickel-based microsphere with the spherical core-nano porous shell composite structure, and carrying out packaging and oxygen-proof storage on the nickel-based microsphere in the absence of oxygen.
Example 2
A preparation method of a nickel-based material with a spherical core-nano porous shell composite structure comprises the following steps:
(1) adding nickel acetate into deionized water, stirring and dissolving to prepare a nickel acetate solution with the molar concentration of 0.05mole/L, then adding PVP (polyvinyl pyrrolidone) with the weight of 1.2% of that of the nickel acetate into the nickel acetate solution, and stirring and dissolving to obtain a mixed solution for later use;
(2) adding oxalic acid into deionized water, stirring and dissolving to prepare an oxalic acid solution with the molar concentration of 0.055 mole/L;
(3) mixing the mixed solution obtained in the step (1) with an oxalic acid solution according to the volume ratio of 1:1, uniformly stirring, quickly dropwise adding ammonia water, adjusting the pH value to 8.0, stirring again, and then standing and culturing for 0.5h at 40 ℃;
(4) after the standing culture is finished, filtering, collecting precipitates, washing the precipitates for multiple times by using deionized water, washing the precipitates once by using absolute ethyl alcohol, and then placing the precipitates in an oven at the temperature of 80 ℃ for drying for 8 hours;
(5) and placing the dried product in a quartz boat, then placing the quartz boat in the middle position of a thermocouple in a tubular atmosphere furnace, filling argon as protective gas into the quartz boat, then carrying out heat treatment for 30min at 350 ℃, cooling to room temperature to obtain the nickel-based microsphere with the spherical core-nano porous shell composite structure, and carrying out packaging and oxygen-proof storage on the nickel-based microsphere in the absence of oxygen.
Example 3
A preparation method of a nickel-based material with a spherical core-nano porous shell composite structure comprises the following steps:
(1) adding nickel acetate into deionized water, stirring and dissolving to prepare a nickel acetate solution with the molar concentration of 0.1mole/L, then adding PVP with the weight of 2% of that of the nickel acetate into the nickel acetate solution, and stirring and dissolving to obtain a mixed solution for later use;
(2) adding oxalic acid into deionized water, stirring and dissolving to prepare an oxalic acid solution with the molar concentration of 0.11 mole/L;
(3) mixing the mixed solution obtained in the step (1) with an oxalic acid solution according to the volume ratio of 1.0:1.5, uniformly stirring, quickly dropwise adding ammonia water, adjusting the pH value to 8.5, stirring again, and then standing and culturing at 60 ℃ for 2 hours;
(4) after the standing culture is finished, filtering, collecting precipitates, washing the precipitates for multiple times by using deionized water, washing the precipitates once by using absolute ethyl alcohol, and then placing the precipitates in a drying oven at the temperature of 95 ℃ for drying for 6 hours;
(5) and placing the dried product in a quartz boat, then placing the quartz boat in the middle position of a thermocouple in a tubular atmosphere furnace, filling hydrogen as protective gas into the quartz boat, then carrying out heat treatment for 15min at 400 ℃, cooling to room temperature to obtain the nickel-based microsphere with the spherical core-nano porous shell composite structure, and carrying out packaging and oxygen-proof storage on the nickel-based microsphere in the absence of oxygen.
The morphological structure of the sample powder prepared in example 2 was observed and analyzed by a field emission scanning electron microscope, and the results are shown in fig. 1, 2, 3 and 4; wherein, fig. 1 and fig. 2 show that the prepared nickel oxalate microsphere has obvious shape structures of spherical cores and spherical radial shells; fig. 3 and 4 show that the prepared nickel-based microspheres have obvious shape structures of spherical cores and nanoporous shells.
Claims (9)
1. A preparation method of a nickel-based material with a spherical core-nano porous shell composite structure is characterized by comprising the following steps:
(1) dissolving nickel acetate in deionized water to prepare a nickel acetate solution with the molar concentration of 0.01-0.10 mol/L, then adding PVP, and stirring to dissolve; wherein the weight of the PVP is 0.5-2% of that of the nickel acetate;
(2) mixing and stirring the solution obtained in the step (1) and an oxalic acid solution with the molar concentration of 0.011-0.11 mol/L, adjusting the pH value to 7.0-8.5, and standing and culturing for 0.5-12 h at the temperature of 20-60 ℃ after stirring; wherein the volume ratio of the oxalic acid solution to the solution obtained in the step (1) is 0.5-1.5: 0.5-1.0;
(3) filtering and collecting precipitates, cleaning for 3-5 times, drying at 70-95 ℃ for 6-12 hours, carrying out heat treatment at 320-400 ℃ for 15-60 min under the protection of protective gas, and cooling to room temperature to obtain the catalyst.
2. The method for preparing a nickel-based material having a spherical core-nanoporous shell composite structure according to claim 1, wherein the molar concentration of the nickel acetate solution in step (1) is 0.05 mol/L.
3. The method for preparing a nickel-based material having a spherical core-nanoporous shell composite structure according to claim 1, wherein the weight of the PVP in step (1) is 1.2% of the weight of the nickel acetate.
4. The method for preparing a nickel-based material having a spherical core-nanoporous shell composite structure according to claim 1, wherein the volume ratio of the oxalic acid solution in the step (2) to the solution obtained in the step (1) is 1: 1.
5. The method for preparing a nickel-based material having a spherical core-nanoporous shell composite structure according to claim 1 or 4, wherein the molar concentration of the oxalic acid solution in step (2) is 0.055 mol/L.
6. The method for preparing a nickel-based material having a spherical core-nanoporous shell composite structure according to claim 1, wherein the culture conditions in step (2) are: adjusting the pH value to 8.0, and performing static culture for 0.5h at the temperature of 40 ℃.
7. The method for preparing a nickel-based material having a spherical core-nanoporous shell composite structure according to claim 1, wherein the heat treatment process in the step (3) is:
and (3) putting the dried precipitate into a quartz boat, putting the quartz boat into the middle position of a tubular atmosphere furnace thermocouple, filling argon or hydrogen serving as protective gas into the quartz boat, and carrying out heat treatment for 15-60 min at 320-400 ℃.
8. The method for preparing a nickel-based material having a spherical core-nanoporous shell composite structure according to claim 1, wherein the cleaning process in the step (3) is:
washing with deionized water for 3-5 times, and finally washing with absolute ethyl alcohol.
9. The nickel-based material with the spherical core-nano porous shell composite structure prepared by the method of any one of claims 1 to 8.
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