CN111945028B - High-porosity micro/nano porous NiO/Ni material and preparation method and special equipment thereof - Google Patents

High-porosity micro/nano porous NiO/Ni material and preparation method and special equipment thereof Download PDF

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CN111945028B
CN111945028B CN202010867718.6A CN202010867718A CN111945028B CN 111945028 B CN111945028 B CN 111945028B CN 202010867718 A CN202010867718 A CN 202010867718A CN 111945028 B CN111945028 B CN 111945028B
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porous
pores
powder
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nial
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CN111945028A (en
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冯培忠
焦欣洋
蔡小平
李周俊
王晓虹
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China University of Mining and Technology CUMT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys

Abstract

A high-porosity micro/nano porous NiO/Ni material and a preparation method and special equipment thereof belong to micro/nano porous materials and preparation methods thereof. The micro/nano porous NiO/Ni material is composed of uniform pores and a continuous framework; the method is characterized in that nickel powder and aluminum powder are used as original powder, and porous NiAl or NiAl with micron-sized pores is synthesized by thermal explosion through the methods of mixing, pressing and vacuum sintering3And (3) putting the sintered blank into 10-30 wt.% of NaOH solution for corrosion, and preparing the porous NiO/Ni material with the nanometer pores and the ligament structure on the framework. The invention combines the preparation advantages of a thermal explosion method and a dealloying method, has simple process operation, short synthesis time, is economic and feasible, and the finally obtained micro/nano porous material has rich pore structure and uniform pore distribution, the porosity is higher than 50%, the micron pore size is between 9 and 30 mu m, the nano pore size is between 30 and 150nm, thereby being beneficial to the application in the fields of catalysis, supercapacitors, lithium ion batteries and the like.

Description

High-porosity micro/nano porous NiO/Ni material and preparation method and special equipment thereof
Technical Field
The invention relates to a micro/nano porous material and a preparation method and special equipment thereof, in particular to a high-porosity micro/nano porous NiO/Ni material and a preparation method and special equipment thereof.
Background
The porous material is a material with a network structure formed by interpenetrated or closed pores, the boundaries or surfaces of the pores are formed by frameworks, and the porous material is a novel material system with integrated functions and structures developed in the 20 th century and is considered as one of important supports for sustainable development and promotion of environment-friendly industrial development. Especially in a coal gasification technical process device, the application of the porous material in the aspect of filtration plays a key role, which has important significance for improving the industrial production efficiency, saving energy, protecting the environment and recycling resources. With the innovation of technology and the continuous update of equipment, the preparation methods of the porous materials are increasingly increased, the preparation process is increasingly simple, the testing means is more and more advanced, the porosity of the porous materials is also improved to more than 80% from a few percent and a dozen, the pore size is also developed into the nanometer pores from the micron pores, and the specific surface area is obviously increased. With the rapid development of science and technology, the application of porous materials is not limited to a single aspect, and is gradually expanding to the fields of filtration, catalysis, supercapacitors, batteries and the like.
The thermal explosion method is one of the technologies for synthesizing porous materials by combustion, and is a new method for preparing porous materials which is rapidly developed in recent years, and the thermal explosion method utilizes chemical reaction released by reactants to thermally synthesize the materials, and generally does not need external energy. When the ignition temperature of the sample is reached, the temperature of the sample rises sharply to the combustion temperature, as in the case of "explosions", the synthesis time is between a few seconds and a few tens of seconds, the pore size of the sample after reaction is between a few microns and a few tens of microns, and the porosity increases significantly, usually above 50%. Although the thermal explosion method technology has the advantages of simple equipment, quick reaction, purer product, high efficiency, low energy consumption and the like, and can adjust the pore diameter characteristic according to different practical application conditions, when the porous Ni-Al intermetallic compound is prepared by adopting the method, the heat release is high, the combustion temperature exceeds the melting point of Ni-Al, so that a sintering blank is melted, pores inside the material present the characteristic of circular closed pores, and the current thermal explosion method is difficult to control the appearance of the Ni-Al sintering blank, so that the thermal explosion technology needs to be optimized to form micron-sized pores with high porosity and uniformity and continuity.
The nano porous metal oxide material has the characteristics of large specific surface area, low density, good chemical stability and the like, and is widely researched and applied in the international material field in the fields of catalysis, sensing, batteries and the like. At present, a porous material with the pore size reaching the nanometer level is difficult to obtain by a powder sintering method, so that the porous material is limited in the fields of electrochemistry, catalysis, energy storage and the like. The dealloying method is also a new method for preparing the nano porous metal oxide emerging in recent years, and the method utilizes the larger electrode potential difference existing among the components, and the electrochemically active metal elements in the alloy are selectively dissolved to form a bicontinuous nano porous structure taking inert metal as a framework, wherein the final structure consists of mutually staggered nano pores and the framework formed by the metal oxide. Therefore, how to combine the current preparation process with the optimized pore structure, further develop a new idea to explore a new pore structure, combine the process advantages of a thermal explosion method and a dealloying method, remove the metal element Al in the Ni-Al-based intermetallic compound skeleton by using a corrosion pore-forming method, form a micro/nano-pore coexisting graded porous material and load some precious metal substances, expect that the porous material has a larger specific surface area, higher activity and adsorption performance, which is also a key scientific problem needing attention at present. At present, research related to preparation of a high-porosity micron-sized porous Al-based intermetallic compound by a combustion synthesis technology and preparation of a micro/nano porous metal oxide by a dealloying method is not available.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a porous NiO/Ni with coexisting high-porosity micro/nano pores and a preparation method thereof, and solves the problems that the appearance and the pore appearance of a Ni-Al sintered blank are difficult to control and nano pores are difficult to prepare on a framework in the conventional combustion synthesis method.
The technical scheme is as follows: the purpose of the invention is realized as follows: the invention comprises a preparation method and special equipment of a high-porosity micro/nano-porous NiO/Ni material and the high-porosity micro/nano-porous NiO/Ni material.
The high-porosity micro/nano porous NiO/Ni material consists of uniform pores and a continuous framework; the pores comprise micro-pores and nano-pores; the porosity is more than 50%.
The micron-sized pores are 9-30 mu m in size.
The size of the nanometer pores is 30-150 nm.
The method takes nickel powder and aluminum powder as raw powder, prepares cylindrical green bodies by mixing and pressing, and synthesizes porous NiAl or NiAl with micron-sized pores by thermal explosion3The material sintering blank adopts special equipment to realize temperature measurement and transparent observation of a sample in the combustion process; and then putting the sintered blank into 10-30 wt.% of NaOH for corrosion, and controlling the concentration and temperature of a corrosive liquid to prepare the porous NiO/Ni material with the nano-scale pores.
The method comprises the following specific steps:
step 1: weighing two kinds of powder according to the atomic ratio of the nickel powder to the aluminum powder of 1:1 or 1:3, and performing ball milling and pressing to obtain a cylindrical powder green compact, wherein a ball milling medium is absolute ethyl alcohol; sintering the powder pressed compact in a tube furnace to prepare porous NiAl or NiAl with complete shape3Sintering the material blank;
step 2: preparing 10-30 wt.% NaOH solution, pouring the NaOH solution into at least two sealed test tubes, and heating each test tube in a water bath kettle at different temperatures, wherein the temperature is set to be 20-80 ℃;
and step 3: the porous NiAl or the NiAl prepared in the step 13Respectively placing the sintered blank into test tubes with solutions of different temperatures, and subjecting the porous NiAl or NiAl to annealing3Corroding the material sintered blank, wherein the reaction is violent in the corrosion process and accompanied with bubbles until no bubbles are generated;
and 4, step 4: and after bubbles are not generated, taking out the sintered blank, cleaning and drying to obtain the porous NiO/Ni material with high porosity and micro/nano pores.
The sintering process of the tube furnace comprises the following steps: firstly, carrying out heat preservation treatment at low temperature, heating to 470-490 ℃ at a heating rate of 8-12 ℃/min, and preserving heat for 1-4 h; continuing to heat to 680-700 ℃, preserving the temperature for 10-30 min, and cooling to room temperature, wherein an obvious thermal explosion reaction can occur at the stage; the sintering environment is a vacuum environment.
The method is characterized in that a special tubular furnace is adopted for preparing the high-porosity micro/nano porous NiO/Ni material, a loading platform is arranged in a furnace chamber of the tubular furnace, refractory bricks are arranged on the loading platform, a sample is placed on the refractory bricks, the sample is a powder pressed compact, and the tubular furnace uniformly heats the sample in a resistance heating mode; the furnace chamber is a glass tube, and flanges are arranged at two ends of the glass tube; the flange at one end is connected with a vacuum pump to ensure that the inside of the furnace cavity is always in a vacuum state, and the flange at the other end is a visible window which is made of transparent glass; the thermocouple wire penetrates through the double-hole corundum tube and penetrates out of the flange through the double-hole corundum tube, the thermocouple wire is connected with the acquisition card, the acquisition card is connected with a computer, and temperature change of a sample, namely a powder pressed compact, is recorded in real time through temperature measurement software in the computer; and a high-resolution camera is arranged outside the visual window, so that the change condition of the powder compact in the sintering process can be observed at any time, data can be stored, and the sample can be observed in a transparent manner.
Has the advantages that: by adopting the technical scheme, the thermal explosion process is optimized, and heat preservation treatment is carried out at a low temperature for a certain time, so that the problems of incomplete appearance and the like of the Ni-Al sintered blank in the reaction heat release process are solved, and a precursor with high porosity and controllable pore structure is prepared; the nanometer pores and the ligament structure are prepared on the porous framework by combining the dealloying method, the preparation process is simple, the pores are rich and uniformly distributed, and the specific surface area is 87.4 m2And above/g, finally forming a novel pore structure of the micron-pore nested nano-pore. In addition, the size of the nanometer pores and ligaments can be adjusted by changing the concentration and the temperature of the corrosive liquid, and the porous NiO/Ni material with nanometer pores is prepared.
The invention creatively combines the thermal explosion method and the dealloying method to prepare the micro/nano porous NiO/Ni material with high porosity and uniformly distributed pores, the porosity is high, the micron-sized pores are uniformly distributed among product frameworks, and the prepared three-dimensional nano nickel-based material can be used as the negative electrode material of the lithium battery. The porous shape improves the specific surface area of the electrode material, the mutually communicated pore channels shorten the diffusion distance of lithium ions, provide sufficient structural space for the flow of the lithium ions and electrons, reduce the charge transfer resistance and the interface impedance in the charging and discharging process, and effectively inhibit the phenomena of electrode material breakage and capacity attenuation caused by volume expansion, thereby being more beneficial to energy storage.
Solves the problems that the existing combustion synthesis method is difficult to control the shape and pore appearance of the Ni-Al sintered blank and is difficult to prepare nano pores on a framework, and achieves the aim of the invention.
The advantages are that: the preparation method is simple in preparation process and short in reaction time, transparent observation and effective control of the pore structure in the synthesis process can be realized, the porosity of the prepared porous material is high, the micron pores are uniformly distributed among NiAl frameworks and have the size of 9-30 mu m, the nanometer pores and the ligament structure are regularly distributed on the frameworks, the size of the nanometer pores is 30-150 nm, and the specific surface area is 84 m2More than g, the lithium ion battery cathode material has better cycle stability and rate capability.
Drawings
FIG. 1 is a schematic diagram of the process of preparing high-porosity micro/nano-porous NiO/Ni material by using a special tube furnace.
FIG. 2(a) is a temperature variation graph of the porous NiAl material prepared by the present invention.
FIG. 2(b) is a BSE diagram of a microporous NiAl material prepared by the present invention.
Fig. 3(a) is an SEM image of a micro/nanoporous material prepared by etching at 20 ℃.
Fig. 3(b) is a partially enlarged SEM picture of the micro/nano-porous material prepared by etching at 20 ℃.
Fig. 3(c) is an SEM image of the micro/nanoporous material prepared by etching at 50 ℃.
Fig. 3(d) is a partial enlarged view of SEM of the micro/nanoporous material prepared by etching at 50 ℃.
FIG. 4 is a diagram showing the electrochemical performance of a sample corroded by NaOH solution at 20 ℃ as a negative electrode material of a lithium ion battery.
In fig. 1, a visual window; 2. collecting cards; 3. a computer; 4. a double-hole corundum tube; 5. an object stage; 6. a thermocouple wire; 7. a refractory brick; 8. a sample; 9. briquetting; 10. a furnace plug; 11. a vacuum pump; 12. a resistance furnace; 13. a camera; 14. the furnace chamber is heated.
Detailed Description
The invention comprises a preparation method and special equipment of a high-porosity micro/nano-porous NiO/Ni material and the high-porosity micro/nano-porous NiO/Ni material.
The high-porosity micro/nano porous NiO/Ni material consists of uniform pores and a continuous framework; the pores comprise micro-pores and nano-pores; the porosity is more than 50%.
The micron-sized pores are 9-30 mu m in size.
The size of the nanometer pores is 30-150 nm.
The method takes nickel powder and aluminum powder as raw powder, prepares cylindrical green bodies by mixing and pressing, and synthesizes porous NiAl or NiAl with micron-sized pores by thermal explosion3The material sintering blank adopts special equipment to realize temperature measurement and transparent observation of a sample in the combustion process; and then putting the sintered blank into 10-30 wt.% of NaOH solution for corrosion, controlling the concentration and temperature of the corrosive solution, and preparing the porous NiO/Ni material with the nano-scale pores.
The method comprises the following specific steps:
step 1: weighing two kinds of powder according to the atomic ratio of the nickel powder to the aluminum powder of 1:1 or 1:3, and performing ball milling and pressing to obtain a cylindrical powder green compact, wherein a ball milling medium is absolute ethyl alcohol; sintering the powder pressed compact in a tube furnace to prepare porous NiAl or NiAl with complete shape3Sintering the material blank;
step 2: preparing 10-30 wt.% NaOH solution, pouring the NaOH solution into at least two sealed test tubes, and heating each test tube in a water bath kettle at different temperatures, wherein the temperature is set to be 20-80 ℃;
and step 3: the porous NiAl or the NiAl prepared in the step 13Respectively placing the sintered blank into test tubes with solutions of different temperatures, and subjecting the porous NiAl or NiAl to annealing3The material sintering blank is corroded, the reaction is violent in the corrosion process and accompanied with the appearance of bubbles,until no more bubbles are generated;
and 4, step 4: and after bubbles are not generated, taking out the sintered blank, cleaning and drying to obtain the porous NiO/Ni material with high porosity and micro/nano pores.
The sintering process of the tube furnace comprises the following steps: firstly, carrying out heat preservation treatment at low temperature, heating to 470-490 ℃ at a heating rate of 8-12 ℃/min, and preserving heat for 1-4 h; continuing to heat to 680-700 ℃, preserving the temperature for 10-30 min, and cooling to room temperature, wherein an obvious thermal explosion reaction can occur at the stage; the sintering environment is a vacuum environment.
The method for preparing the high-porosity micro/nano porous NiO/Ni material adopts a special tube furnace which comprises a heating furnace chamber 14 and a resistance furnace 12, wherein an object carrying table 5 is arranged in the heating furnace chamber 14, a refractory brick 7 is arranged on the object carrying table 5, a sample 8 is placed on the refractory brick 7, the sample 8 is a powder pressed compact, a pressed block 9 is arranged on the powder pressed compact, the powder pressed compact is ensured not to be displaced in the heating process and is in the temperature measuring range of a thermocouple wire all the time, and the resistance furnace 12 uniformly heats the sample 8; the heating furnace chamber 14 is a glass tube, and flanges are arranged at two ends of the glass tube; the flange at one end is connected with the vacuum pump 11 to ensure that the inside of the furnace chamber 14 is always in a vacuum state, the flange at the other end is a visible window 1, and the visible window 1 is made of transparent glass; the thermocouple wire 6 penetrates through the double-hole corundum tube 4 and penetrates out of the flange through the double-hole corundum tube 4, the thermocouple wire 6 is connected with the acquisition card 2, the acquisition card 2 is connected with the computer 3, and temperature change of the sample 8, namely the powder pressed compact, is recorded in real time through temperature measurement software in the computer 3; a high-resolution camera 13 is arranged outside the visual window 1, so that the change condition of the powder compact in the sintering process can be observed at any time, data can be stored, and the sample 8 can be observed in a transparent mode.
Embodiments of the present application are further described below with reference to the following drawings:
example 1, weighing raw materials according to the atom ratio of nickel powder to aluminum powder of 1:1, for example, respectively taking 11.8g of nickel powder and 5.4g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling tank for uniform mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; and (3) putting the NiAl material into a vacuum tube furnace for heating, firstly heating to 480 ℃ at the heating rate of 10 ℃/min, preserving heat for 3h, then continuously heating to 700 ℃ and preserving heat for 10min to obtain the micron porous NiAl material with high porosity and complete appearance. Preparing 20 wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 20 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.
In the attached figure 1, (a) is an equipment diagram for preparing a micron porous NiAl material, wherein a flange at one end is connected with a vacuum pump, and a flange at the other end is transformed into a transparent visual window and is connected with temperature measurement software on a computer through a collection card; in the attached figure 1, (b) is a porous NiAl sintered blank; in fig. 1, (c) is a schematic diagram of the process of corroding sintered compact in a centrifuge tube filled with 20 wt.% NaOH solution; in FIG. 1, (d) is a schematic representation of the completion of the etching of the sintered compact in a centrifuge tube containing a 20 wt.% NaOH solution.
In FIG. 2, FIG. 2(a) is a temperature change curve of a sample heated at a temperature rise rate of 10 ℃/min and FIG. 2(b) is a corresponding BSE image.
FIG. 3 is a scanning electron micrograph of the micro/nanoporous NiO/Ni prepared in accordance with the present invention. Wherein: fig. 3(a) is an SEM image of a micro/nano-porous material prepared by etching at 20 ℃ and fig. 3(b) is a partially enlarged view of an SEM image of a micro/nano-porous material prepared by etching at 20 ℃.
FIG. 4 is a graph showing the electrochemical performance test of a sample corroded in NaOH solution at 20 ℃ as a negative electrode material of a lithium ion battery. Wherein: FIG. 4(a) is a CV curve of a micro/nanoporous material prepared by etching at 20 ℃; FIG. 4(b) constant current charge and discharge curves; FIG. 4(c) rate performance curve and FIG. 4(d) cycle performance curve.
Example 2 weighing raw materials according to the atom ratio of nickel powder to aluminum powder of 1:1, for example, respectively taking 11.8g of nickel powder and 5.4g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot for uniform mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; and (3) putting the NiAl material into a vacuum tube furnace for heating, firstly heating to 480 ℃ at the heating rate of 10 ℃/min, preserving heat for 3h, then continuously heating to 700 ℃ and preserving heat for 10min to obtain the micron porous NiAl material with high porosity and complete appearance. Preparing 20 wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 50 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.
In fig. 3, fig. 3(c) is an SEM and (d) a partial enlarged view of the micro/nano porous material prepared by etching at 50 ℃.
Example 3 weighing raw materials according to the atomic ratio of nickel powder to aluminum powder of 1:1, for example, respectively taking 11.8g of nickel powder and 5.4g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot, uniformly mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; and (3) putting the NiAl material into a vacuum tube furnace for heating, firstly heating to 480 ℃ at the heating rate of 10 ℃/min, preserving heat for 3h, then continuously heating to 700 ℃ and preserving heat for 10min to obtain the micron porous NiAl material with high porosity and complete appearance. Preparing 20 wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 80 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.
Example 4:weighing raw materials according to the atom ratio of nickel powder to aluminum powder of 1:3, for example, respectively taking 11.8g of nickel powder and 16.2g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling tank for uniformly mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; heating in a vacuum tube furnace at a heating rate of 8 deg.C/min to 470 deg.C for 4h, heating to 700 deg.C for 10min to obtain porous NiAl with high porosity and complete shape3A material. Preparing 10 wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 20 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.
Example 5 weighing the raw materials according to the atom ratio of the nickel powder to the aluminum powder of 1:3, for example, respectively taking 11.8g of nickel powder and 16.2g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot for uniform mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; heating in a vacuum tube furnace at a heating rate of 8 deg.C/min to 470 deg.C for 4h, heating to 700 deg.C for 10min to obtain porous NiAl with high porosity and complete shape3A material. Preparing 10 wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 50 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.
Example 6 weighing the raw materials according to the atom ratio of the nickel powder to the aluminum powder of 1:3, for example, respectively taking 11.8g of nickel powder and 16.2g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot for uniform mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; heating in a vacuum tube furnace at a heating rate of 8 deg.C/min to 470 deg.C for 4h, heating to 700 deg.C for 10min to obtain porous NiAl with high porosity and complete shape3A material. Preparing 10 wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 80 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.
Example 7 weighing the raw materials according to the atomic ratio of nickel powder to aluminum powder of 1:3, for example, respectively taking 11.8g of nickel powder and 16.2g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot for uniform mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; heating in a vacuum tube furnace at a heating rate of 10 deg.C/min to 480 deg.C for 3h, heating to 700 deg.C for 10min to obtain porous NiAl with high porosity and complete shape3A material. Preparing 20 wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 20 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.
Example 8 weighing the raw materials according to the atomic ratio of nickel powder to aluminum powder of 1:3, for example, respectively taking 11.8g of nickel powder and 16.2g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot for uniform mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; heating in a vacuum tube furnace at a heating rate of 10 deg.C/min to 480 deg.C for 3h, heating to 700 deg.C for 10min to obtain porous NiAl with high porosity and complete shape3A material. Preparing 20 wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 50 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.
Example 9 weighing the raw materials according to the atomic ratio of nickel powder to aluminum powder of 1:3, for example, respectively taking 11.8g of nickel powder and 16.2g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot for uniform mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; heating in a vacuum tube furnace at a heating rate of 10 deg.C/min to 480 deg.C for 3h, heating to 700 deg.C for 10min to obtain porous NiAl with high porosity and complete shape3A material. Preparing 20 wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 80 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample by using alcohol and deionized water, cleaning the sample by using ultrasonic waves for 20min, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni materialAnd (5) feeding.
Example 10 weighing raw materials according to the atomic ratio of nickel powder to aluminum powder of 1:3, for example, respectively taking 11.8g of nickel powder and 16.2g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot, uniformly mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; heating in a vacuum tube furnace at a heating rate of 12 deg.C/min to 490 deg.C for 1 h, heating to 680 deg.C, and maintaining for 30min to obtain porous NiAl with high porosity and complete shape3A material. Preparing 30wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 20 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.
Example 11 weighing the raw materials according to the atomic ratio of nickel powder to aluminum powder of 1:3, for example, respectively taking 11.8g of nickel powder and 16.2g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot for uniform mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; heating in a vacuum tube furnace at a heating rate of 12 deg.C/min to 490 deg.C for 1 h, heating to 680 deg.C, and maintaining for 30min to obtain porous NiAl with high porosity and complete shape3A material. Preparing 30wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 50 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample with ultrasonic waves for 20min, and drying the sample in a vacuum drying oven for one night to obtain the sintered blank with high porosity and micro poresA nanoporous NiO/Ni material.
Example 12 weighing the raw materials according to the atom ratio of the nickel powder to the aluminum powder of 1:3, for example, respectively taking 11.8g of nickel powder and 16.2g of aluminum powder, pouring the nickel powder and the aluminum powder into a ball milling pot for uniform mixing for 4 hours, and taking absolute ethyl alcohol as a ball milling medium; pouring the ball-milled mixed solution into a beaker, and putting the beaker into a drying box for drying for 24 hours; weighing about 0.3g of the mixed powder, pouring the mixed powder into a specific mold for pressing to obtain a cylindrical green body with d10mm multiplied by 1 mm; heating in a vacuum tube furnace at a heating rate of 12 deg.C/min to 490 deg.C for 1 h, heating to 680 deg.C, and maintaining for 30min to obtain porous NiAl with high porosity and complete shape3A material. Preparing 30wt.% NaOH corrosive liquid, cooling the NaOH corrosive liquid to room temperature along with a furnace, putting the cleaned and dried sintered blank into a test tube filled with the corrosive liquid, putting the test tube into a water bath kettle with a preset temperature, wherein the temperature is 80 ℃ until bubbles are not generated, taking out a sample, exchanging and washing the sample with alcohol and deionized water, cleaning the sample for 20min by ultrasonic waves, and putting the cleaned sample into a vacuum drying box for drying overnight to obtain the high-porosity micro/nano-porous NiO/Ni material.

Claims (2)

1. A high-porosity micro/nano porous NiO/Ni material is characterized in that: the high-porosity micro/nano porous NiO/Ni material consists of uniform pores and a continuous framework; is a composite material; the pores comprise micro-pores and nano-pores; the porosity is more than 50%;
the size of the micron-sized pores is 9-30 mu m;
the size of the nanometer pores is 30-150 nm.
2. The method for preparing the high-porosity micro/nano-porous NiO/Ni material according to claim 1, which is characterized in that: the method takes nickel powder and aluminum powder as raw powder, prepares cylindrical green bodies by mixing and pressing, and synthesizes porous NiAl or NiAl with micron-sized pores by thermal explosion3The material sintering blank block adopts special equipment to realize temperature measurement and transparent observation of a sample in the combustion process; however, the device is not suitable for use in a kitchenThen, putting the sintered blank into 10-30 wt.% of NaOH solution for corrosion, controlling the concentration and temperature of a corrosive solution, and preparing a porous NiO/Ni material with nano-scale pores;
the method comprises the following specific steps:
step 1: weighing two kinds of powder according to the atomic ratio of the nickel powder to the aluminum powder of 1:1 or 1:3, and performing ball milling and pressing to obtain a cylindrical powder green compact, wherein a ball milling medium is absolute ethyl alcohol; sintering the powder pressed compact in a tube furnace to prepare porous NiAl or NiAl with complete shape3Sintering the material blank;
step 2: preparing 10-30 wt.% NaOH solution, pouring the NaOH solution into at least two sealed test tubes, and heating each test tube in a water bath kettle at different temperatures, wherein the temperature is set to be 20-80 ℃;
and step 3: the porous NiAl or the NiAl prepared in the step 13Respectively placing the sintered blank into test tubes with solutions of different temperatures, and subjecting the porous NiAl or NiAl to annealing3Corroding the material sintered blank, wherein the reaction is violent in the corrosion process and accompanied with bubbles until no bubbles are generated;
and 4, step 4: after bubbles are not generated, taking out the sintered blank, cleaning and drying to obtain the porous NiO/Ni material with high porosity and micro/nano pores;
the sintering process of the tube furnace comprises the following steps: firstly, carrying out heat preservation treatment at low temperature, heating to 470-490 ℃ at a heating rate of 8-12 ℃/min, and preserving heat for 1-4 h; continuing to heat to 680-700 ℃, preserving the temperature for 10-30 min, and cooling to room temperature, wherein an obvious thermal explosion reaction can occur at the stage; the sintering environment is a vacuum environment.
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