CN109967735B - Method for preparing copper fiber felt by taking graphene as template - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/062—Fibrous particles
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- 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
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- 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
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- B22F3/11—Making porous workpieces or articles
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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Abstract
The invention belongs to the technical field of metal fiber felts, and particularly relates to a method for preparing a copper fiber felt by taking graphene as a template, which comprises the following steps: step 1) preparation of precursor solution; 2) carrying out freeze drying treatment; 3) and (4) high-temperature heat treatment. The preparation method of the invention uses CuCl2As a copper source, with Ar and NH3The mixed gas of (A) is a reducing agent, NH3Gas exchange of CuCl2Reducing the copper elementary substance particles into copper elementary substance particles, capturing the copper elementary substance particles by graphene, and successfully preparing the copper fiber felt consisting of copper fibers with the average diameter of 2-8 mu m through heat treatment at 950-1050 ℃. The copper fiber felt has a porous structure and a large specific surface area, and has a prospect of being applied to bone implants, lithium metal batteries, fuel cells, catalysts, catalyst carriers, filtering and separating materials, heat exchangers, oil-water separating materials and the like.
Description
Technical Field
The invention belongs to the technical field of metal fiber felts, and particularly relates to a method for preparing a copper fiber felt by taking graphene as a template.
Background
Metal fiber (sintered) mats are made of metal fibers and the mat structure is formed by forming sintered necks at the overlap points of the metal fibers. The material of the metal fiber (sintered) felt comprises stainless steel, carbon steel, cast iron, copper, aluminum, nickel and the like. The traditional copper fiber felt has a porous structure, certain mechanical property and physical and chemical properties, becomes a novel structure/function integrated material, and has a prospect of being applied as bone implants, lithium metal batteries, fuel cells, catalysts, catalyst carriers, filtering and separating materials, heat exchangers, oil-water separating materials and the like. The typical preparation process of the traditional copper fiber felt is[1–3]: (1) cutting copper fibers from the surface of the copper rod by using a lathe (such as a multi-tooth cutting tool); (2) classifying the obtained copper fibers according to the length-diameter ratio, mixing, spreading in a stainless steel mold, and filling Al2O3The powder is used for keeping certain porosity; (3) installing an upper cover of the stainless steel mold and fastening by using bolts; (4) placing the stainless steel mold in an atmosphere furnace under a weakly reducing atmosphere (e.g., H)2Air atmosphere) and micro-positive pressure (such as 0.3MPa) at 850-950 ℃ for 30-60 min; (5) after cooling with the furnace, the sample was taken out and then washed to remove Al2O3And (5) obtaining the traditional copper fiber felt.
The typical preparation process of the traditional copper fiber felt has certain defects: 1) the process is complex and the cost is high; 2) due to Al2O3Use of powders of Al during heat treatment2O3And/or Al particles (Al)2O3Reduced to elemental Al) adhere to the surface of the copper fibers, which as impurities may impair the physicochemical properties of conventional copper fiber mats; 3) the diameter of the copper fibers in the conventional copper fiber mat is large, which is usually equal to or greater than 100 μm, thereby reducing the specific surface area of the conventional copper fiber mat.
Reference to the literature
[1]Yong Tang,Wei Yuan.Minqiang Pan and Zhenping Wan,Feasibility study of porous copper fiber sintered felt:A novel porous flow field in proton exchange membrane fuel cells.International Journal of Hydrogen Energy 2010;35:9661–9677.
[2] The preparation method of the super-hydrophobic/super-oleophilic oil-water separation copper fiber felt is invented in Chinese patent No. 201410846141.5.
[3] A copper fiber felt material with a nano-porous surface structure and a preparation method thereof, China invention patent, 201410637659.8.
Disclosure of Invention
Aiming at the defects of the typical preparation process of the traditional copper fiber felt, the invention discloses a method for preparing the copper fiber felt by using graphene as a template, the preparation method is simplified in process and low in cost, the diameter of copper fibers in the obtained copper fiber felt is small, and the average value of the diameter is 2-8 mu m.
The technical scheme of the invention is as follows:
the method for preparing the copper fiber felt by taking the graphene as the template comprises the following steps:
1) preparing a precursor solution:
(1) adding CuCl2·2H2Dissolving O in deionized water or distilled water to obtain CuCl2A solution;
(2) to CuCl2Adding absolute ethyl alcohol and graphene powder into the solution to obtain a graphene suspension I;
(3) sequentially carrying out ultrasonic treatment, vacuum treatment and ultrasonic treatment on the graphene suspension IAnd (4) treating until the graphene is completely immersed in the CuCl2Obtaining a graphene suspension II through solution;
2) and (3) freeze drying treatment: freeze-drying the graphene suspension II obtained in the step 1) for 24-36 h to obtain the loaded CuCl2The graphene powder of (1);
3) high-temperature heat treatment:
(1) putting the powder obtained in the step 2) into two porcelain boats or quartz boats which are buckled up and down;
(2) placing the two ceramic or quartz boats in a tube furnace;
(3) heating the tube furnace to 550-650 ℃ in Ar gas atmosphere;
(4) the Ar gas is turned off, and Ar and NH are simultaneously turned on3Mixed gas of (1), NH in mixed gas3The content is 30-60%, and the tube furnace is kept at 550-650 ℃ for 15-25 min;
(5) ar and NH3Closing the mixed gas, simultaneously opening Ar gas, heating the tube furnace to 950-1050 ℃, and preserving heat for 30-60 min;
(6) and cooling the tube furnace to room temperature in Ar atmosphere to obtain the copper fiber felt.
Graphene and CuCl in the step 1)2·2H2The mass ratio of O, deionized water or distilled water to absolute ethyl alcohol is 1: 28-56: 400-1700: 100-200.
The ultrasonic treatment condition is 200-2500W ultrasonic treatment for 5-30 min.
The vacuum treatment condition is 0.0001-0.01 MPa for 3-10 min.
The air inlet ends of the two porcelain or quartz boats in the step 3) are reserved for 5-40 mm2The gap of (2).
Ar gas, Ar and NH3The flow rate of the mixed gas is 5-40 mL/min.
The temperature rise rate of the tubular furnace is 5-40 ℃/min.
We have found that in the present invention, when the heat treatment temperature is 550-650 ℃, CuCl is present2Is covered with NH3The gas is reduced into copper simple substance particles, and the copper simple substance particles are captured by the graphene under the drive of the carrier gasAnd the captured copper simple substance particles are used as a secondary template to further capture floating copper simple substance particles, so that copper fibers are formed at 950-1050 ℃, and sintering necks are formed at the lap joints of the copper fibers to form a copper fiber felt. Meanwhile, the graphene is gradually discharged out of the tube furnace under the driving of the carrier gas.
Compared with the prior art, the invention has the advantages and positive effects that:
(1) the invention reports a method for preparing a copper fiber felt by using graphene as a template, and compared with the traditional preparation process of the copper fiber felt, the method disclosed by the invention is simple in process.
(2) The preparation method reported by the invention does not use Al2O3Powder, so that Al is not introduced to the surface of the copper fiber2O3And/or Al particulate impurities.
(3) Compared with the traditional copper fiber felt, the copper fiber felt is small in diameter, the average value of the copper fiber in the copper fiber felt is 2-8 mu m, and therefore the specific surface area of the copper fiber felt is large, and the exposure of active sites of the copper fiber felt is facilitated.
(4) In the high-temperature heat treatment process of the preparation method reported by the invention, the heating rate is high, and the energy and the time are saved.
Drawings
Fig. 1 is an XRD pattern of the copper fiber mat prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the surface topography of the copper fiber mat prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated and described with reference to the following examples, which are not intended to limit the invention in any way. The starting materials used in the following examples are all commercially available analytical pure materials.
Example 1
1) Preparing a precursor solution:
(1) 14g of CuCl2·2H2O was dissolved in 425g deionized water to give CuCl2A solution;
(2) to CuCl2Adding 50g of absolute ethyl alcohol and 0.25g of graphene powder into the solution to obtain graphene suspensionI;
(3) Sequentially carrying out 2000W ultrasonic treatment on the graphene suspension I for 15min, 0.001MPa vacuum treatment for 7min and 1500W ultrasonic treatment for 15min until the graphene is completely immersed in CuCl2And (5) obtaining a graphene suspension II. Graphene and CuCl in precursor solution2·2H2The mass ratio of O, distilled water and absolute ethyl alcohol is 1: 56: 1700: 200.
2) and (3) freeze drying treatment: freeze-drying the graphene suspension II obtained in the step 1) for 36h to obtain the loaded CuCl2The graphene powder of (3).
3) High-temperature heat treatment:
(1) placing the powder obtained in the step 2) into two quartz boats which are buckled up and down, wherein the air inlet ends of the two quartz boats are reserved for 20mm2The gap of (2);
(2) placing the two quartz boats in a microwave tube furnace;
(3) heating a microwave tube furnace to 600 ℃ at the speed of 35 ℃/min in an Ar gas atmosphere with the flow rate of 5 mL/min;
(4) closing Ar gas, and simultaneously opening Ar and NH3Mixed gas of (1), NH in mixed gas3The content of the mixed gas is 50 percent, the flow rate of the mixed gas is 10mL/min, and the microwave tube furnace is kept at 600 ℃ for 25 min;
(5) turn off Ar and NH3Opening Ar gas at the same time, wherein the flow rate of the Ar gas is 15mL/min, heating the microwave tube furnace to 1000 ℃ at the speed of 40 ℃/min, and preserving the heat for 60 min;
(6) and continuously cooling the microwave tube furnace to room temperature in an Ar gas atmosphere with the flow rate of 25mL/min to obtain the copper fiber felt.
The XRD pattern of the prepared copper fiber felt is shown in figure 1, all diffraction peaks in the pattern belong to elemental copper (JCPDS04-0836), and the copper fiber felt is shown to be composed of the elemental copper. An SEM image of the surface topography of the copper fiber mat is shown in FIG. 2, wherein the copper fiber mat contains a large number of micron-sized holes, and the diameter of the copper fiber is 5.4 +/-2.1 μm.
Example 2
1) Preparing a precursor solution:
(1) 10.5g of CuCl2·2H2O solutionDissolving in 250g of distilled water to obtain CuCl2A solution;
(2) to CuCl2Adding 37.5g of absolute ethyl alcohol and 0.25g of graphene powder into the solution to obtain a graphene suspension I;
(3) sequentially carrying out 2500W ultrasonic treatment on the graphene suspension I for 10min, 0.0001MPa vacuum treatment for 3min and 1000W ultrasonic treatment for 25min until the graphene is completely immersed in CuCl2Obtaining a graphene suspension II through solution; graphene and CuCl in precursor solution2·2H2The mass ratio of O, deionized water and absolute ethyl alcohol is 1: 42: 1000: 150.
2) and (3) freeze drying treatment: freeze-drying the graphene suspension II obtained in the step 1) for 30h to obtain the loaded CuCl2The graphene powder of (3).
3) High-temperature heat treatment:
(1) placing the powder obtained in the step 2) into two quartz boats which are buckled up and down, wherein the air inlet ends of the two quartz boats are reserved for 5mm2The gap of (2);
(2) placing the two quartz boats in a microwave tube furnace;
(3) heating a microwave tube furnace to 550 ℃ at the speed of 25 ℃/min in an Ar gas atmosphere with the flow rate of 10 mL/min;
(4) closing Ar gas, and simultaneously opening Ar and NH3Mixed gas of (1), NH in mixed gas3The content of the mixed gas is 30 percent, the flow rate of the mixed gas is 20mL/min, and the microwave tube furnace is kept at 550 ℃ for 20 min;
(5) turn off Ar and NH3Opening Ar gas at the same time, wherein the flow rate of the Ar gas is 30mL/min, heating the microwave tube furnace to 950 ℃ at the speed of 30 ℃/min, and preserving the heat for 45 min;
(6) and continuously cooling the microwave tube furnace to room temperature in Ar gas atmosphere with the flow rate of 15mL/min to obtain the copper fiber felt.
The XRD pattern of the prepared copper fiber felt shows that the copper fiber felt is composed of simple substance copper. SEM images of the surface topography of the copper fiber felt show that the copper fiber felt contains a large number of micron-sized holes, and the diameter of the copper fiber is 5.0 +/-2.6 microns.
Example 3
1) Preparing a precursor solution:
(1) 28g of CuCl2·2H2O was dissolved in 400g of distilled water to give CuCl2A solution;
(2) to CuCl2Adding 100g of absolute ethyl alcohol and 1g of graphene powder into the solution to obtain a graphene suspension I;
(3) carrying out ultrasonic treatment on the graphene suspension liquid at 200W for 30min, carrying out vacuum treatment at 0.01MPa for 10min and carrying out ultrasonic treatment at 800W for 5min in sequence until the graphene is completely immersed in CuCl2Obtaining a graphene suspension II through solution; graphene and CuCl in precursor solution2·2H2The mass ratio of O, distilled water and absolute ethyl alcohol is 1: 28: 400: 100.
2) and (3) freeze drying treatment: freeze-drying the graphene suspension II obtained in the step 1) for 24 hours to obtain the loaded CuCl2The graphene powder of (3).
3) High-temperature heat treatment:
(1) placing the powder obtained in the step 2) into two porcelain boats which are buckled up and down, and reserving 40mm between the air inlet ends of the two porcelain boats2The gap of (2);
(2) placing the two ceramic boats in a common (electric heating wire) tube furnace;
(3) in the Ar gas atmosphere with the flow rate of 35mL/min, heating a common tube furnace to 650 ℃ at the speed of 5 ℃/min;
(4) closing Ar gas, and simultaneously opening Ar and NH3Mixed gas of (1), NH in mixed gas3The content of the mixed gas is 60 percent, the flow rate of the mixed gas is 40mL/min, and a common tube furnace is kept at 650 ℃ for 15 min;
(5) turn off Ar and NH3Opening Ar gas at the same time, wherein the flow rate of the Ar gas is 38mL/min, heating the common tube furnace to 1050 ℃ at the speed of 10 ℃/min, and preserving the heat for 30 min;
(6) and continuously cooling the common tube furnace to room temperature in Ar gas atmosphere with the flow rate of 30mL/min to obtain the copper fiber felt.
The XRD pattern of the prepared copper fiber felt shows that the copper fiber felt is composed of simple substance copper. SEM images of the surface topography of the copper fiber felt show that the copper fiber felt contains a large number of micron-sized holes, and the diameter of the copper fiber is 4.2 +/-1.7 microns.
Although the method and the manufacturing technique of the present invention have been described by way of preferred embodiments, it is obvious to those skilled in the art that the method and the manufacturing technique described herein can be modified or recombined to realize the final manufacturing technique without departing from the content, spirit and scope of the present invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (7)
1. The method for preparing the copper fiber felt by taking the graphene as the template is characterized by comprising the following steps of:
1) preparing a precursor solution:
(1) adding CuCl2·2H2Dissolving O in deionized water or distilled water to obtain CuCl2A solution;
(2) to CuCl2Adding absolute ethyl alcohol and graphene powder into the solution to obtain a graphene suspension I;
(3) sequentially carrying out ultrasonic treatment, vacuum treatment and ultrasonic treatment on the graphene suspension I until the graphene is completely immersed in CuCl2Obtaining a graphene suspension II through solution;
2) and (3) freeze drying treatment: freeze-drying the graphene suspension II obtained in the step 1) for 24-36 h to obtain the loaded CuCl2The graphene powder of (1);
3) high-temperature heat treatment:
(1) loading CuCl obtained in the step 2)2The graphene powder is placed in two porcelain or quartz boats which are buckled up and down;
(2) placing the two ceramic or quartz boats in a tube furnace;
(3) heating the tube furnace to 550-650 ℃ in Ar gas atmosphere;
(4) the Ar gas is turned off, and Ar and NH are simultaneously turned on3Mixed gas of (1), NH in mixed gas3The content is 30-60%, and the tube furnace is kept at 550-650 ℃ for 15-25 min;
(5) ar and NH3Closing the mixed gas, simultaneously opening Ar gas, heating the tube furnace to 950-1050 ℃, and preserving heat for 30-60 min;
(6) and cooling the tube furnace to room temperature in Ar atmosphere to obtain the copper fiber felt.
2. The method as claimed in claim 1, wherein the graphene powder and CuCl in step 1) are selected from the group consisting of2·2H2The mass ratio of O, deionized water or distilled water to absolute ethyl alcohol is 1: 28-56: 400-1700: 100-200.
3. The method according to claim 1, wherein the ultrasonic treatment is carried out under 200 to 2500W for 5 to 30 min.
4. The method according to claim 1, wherein the vacuum treatment is performed under a vacuum condition of 0.0001 to 0.01MPa for 3 to 10 min.
5. The method as claimed in claim 1, wherein the inlet ends of the two porcelain or quartz boats in step 3) are retained for 5-40 mm2The gap of (2).
6. The method of claim 1, wherein Ar gas, Ar gas and NH are used3The flow rate of the mixed gas is 5-40 mL/min.
7. The method as set forth in claim 1, wherein the temperature rise rate of the tube furnace in the step 3) is 5 to 40 ℃/min.
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