CN111785979A - Metal alloy-carbon nano tube network macroscopic body composite material, preparation method and application thereof - Google Patents
Metal alloy-carbon nano tube network macroscopic body composite material, preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
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- H—ELECTRICITY
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- 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
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- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The invention discloses a metal alloy-carbon nanotube network macroscopic body composite material, a preparation method and application thereof. The preparation method comprises the following steps: providing a carbon nanotube network macroscopic body, wherein the carbon nanotube network macroscopic body contains a simple substance of iron as a trace impurity; activating the carbon nano tube network macroscopic body; contacting the activated carbon nanotube network macroscopic body with a metal precursor solution to perform a displacement reaction on an iron simple substance and the metal precursor to generate a metal simple substance combined with the iron simple substance, wherein the metal simple substance has oxygen reduction catalytic activity, and then performing drying treatment; and finally, carrying out transient electric heating to obtain the composite material. The preparation method provided by the invention is low in cost, simple and feasible, and short in time consumption, the obtained composite material has strong bonding action force between the carbon nanotube network macroscopic body and the metal alloy nanoparticles, excellent catalytic performance and strong stability, has excellent methanol poisoning resistance, and can be directly used as an oxygen electrode for a metal air battery.
Description
Technical Field
The invention relates to an oxygen function electrocatalysis electrode, in particular to a metal alloy-carbon nano tube network macroscopic body composite material and a preparation method thereof, and application of the composite material in preparation of an oxygen electrode, belonging to the technical field of energy and cleaning.
Background
Metal-air batteries have received much attention from researchers due to their high specific energy density, renewable, safe characteristics, and one of the challenges in the development of metal-air batteries is the search for high performance oxygen functional catalysts. The current commercial 20 wt% platinum carbon oxygen reduction catalyst is a carbon material with high specific surface area loaded with platinum nano-particles, and due to the problems of weak interaction force of the platinum nano-particles and carbon and oxidation corrosion of the carbon carrier, the peeling and agglomeration of the platinum nano-particles in the catalyst are easy to occur in the process of long-time or recycling use, so that the service life of the commercial platinum carbon catalyst is shortened. The commercial platinum-carbon catalyst also has the defects of high price, high cost, poor stability and poor methanol poisoning resistance. In order to reduce the cost of the catalyst and optimize the catalytic performance, a platinum-based alloy catalyst with low platinum content prepared by substituting platinum with non-noble metal is one of the methods for developing a high-performance catalyst, the activity of the platinum-based alloy catalyst is greatly improved due to the structural change of Pt electrons in the alloy, the Pt-based alloy catalyst can be prepared by decomposing or reducing a precursor, and how to prepare a Pt-based alloy catalyst with small size, high efficiency, stability and high utilization rate is still the bottleneck of development. Sun et al (J.Am.chem.Soc.2010,132,4996.structural Ordered FePtNanoparticles and Their Enhanced Catalysis for Oxygen Reduction Reaction) prepared monodisperse nano PtM particles (M ═ Fe, Co, Ni, Cu, Zn) based on platinum acetylacetonate and iron acetylacetonate precursors in an oleic acid, oleylamine organic system showed excellent Oxygen Reduction catalytic performance. Wei et al (adv. Mater.2016,28,10673, Structural Evolution of Solid Pt Nanoparticles to a Hollow PtFe Alloy with aPt-Skin Surface via Space-defined Pyrolysis and the Nanoscale Kirkendall Effect) utilize Space-limited Pyrolysis and the Nanoscale Kirkendall effect to convert Pt Nanoparticles into Hollow PtFe alloys with Pt Skin. In addition, there has been much research effort on developing other binary or multicomponent metal alloy nanocatalysts, such as Pb-Fe (Nano Energy 2018,50,70.Atomic registration from distributed Ordered Pd-Fe nanocatalysts with trace emission of Pt definition for electronic analysis), Pt-Fe-Cu (Chemistry of Materials,2018,30,5987.Copper-induced formulation of structural Ordered Pt-Fe-Cu electrochemical interaction with Tunable Phase and engineered Stability), IrM (M: Fe/Co/Ni/Cu) (Nano Energy 2016,29,261-267. catalytic interaction with porous Phase and engineered Stability), Nano Energy or carbon Nano-oxide nanocatalysts, which are commonly used in the field of fuel cells, such as fuel cells, the high surface energy of the metal alloy at the nanoscale is prone to agglomeration and migration, thereby reducing the catalytic performance and the poisoning resistance. Moreover, the currently developed alloy catalyst preparation process is complex and time-consuming, and in addition, when the catalyst is applied to an actual device, most of the catalyst is powder materials which need to be dispersed in a carbon carrier and further loaded in a porous electrode to prepare an oxygen electrode, so that the high utilization rate of the nano catalyst and the high bonding property of the carbon carrier cannot be ensured. Therefore, the bonding force of the alloy nano catalyst and the carbon carrier is improved, and the preparation of the stably-loaded self-supporting electrode is very important for developing the metal-air battery.
Disclosure of Invention
The invention mainly aims to provide a metal alloy-carbon nanotube network macroscopic body composite material and a preparation method thereof, so as to overcome the defects in the prior art.
The invention mainly aims to provide an application of a metal alloy-carbon nanotube network macroscopic body composite material in preparation of an oxygen electrode or a metal-air battery.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a metal alloy-carbon nanotube network macroscopic body composite material, which comprises the following steps:
(1) providing a carbon nanotube network macroscopic body, wherein the carbon nanotube network macroscopic body contains a simple substance of iron as a trace impurity;
(2) activating the carbon nano tube network macroscopic body;
(3) contacting the activated carbon nanotube network macroscopic body with a metal precursor solution to perform a displacement reaction on the iron simple substance and the metal precursor to generate a metal simple substance combined with the iron simple substance, wherein the metal simple substance has oxygen reduction catalytic activity, and then performing drying treatment;
(4) and (4) performing transient electric heating on the carbon nano tube network macroscopic body treated in the step (3) to obtain the metal alloy-carbon nano tube network macroscopic body composite material.
The embodiment of the invention also provides the metal alloy-carbon nanotube network macroscopic body composite material prepared by the method.
The embodiment of the invention also provides a metal alloy-carbon nanotube network macroscopic body composite material which comprises a carbon nanotube network macroscopic body and metal alloy nanoparticles, wherein the metal alloy nanoparticles are uniformly loaded in the carbon nanotube network of the carbon nanotube network macroscopic body, and the metal alloy nanoparticles comprise a Fe simple substance and a metal simple substance with oxygen reduction catalytic activity.
The embodiment of the invention also provides application of the metal alloy-carbon nanotube network macroscopic body composite material in preparation of an oxygen electrode or a metal-air battery.
Correspondingly, the embodiment of the invention also provides an oxygen functional electrocatalytic electrode (oxygen electrode) which comprises the metal alloy-carbon nanotube network macroscopic body composite material.
Correspondingly, the embodiment of the invention also provides a metal-air battery which comprises the metal alloy-carbon nanotube network macroscopic body composite material or the oxygen electrode.
Compared with the prior art, the invention has the advantages that:
1) the preparation method of the metal alloy-carbon nanotube network macroscopic body composite material provided by the invention has the advantages of low cost, simplicity, practicability and short time consumption, and the preparation process of electric heating alloying only needs less than one second;
2) the preparation method of the metal alloy-carbon nanotube network macroscopic body composite material provided by the invention utilizes a functional treatment means to anchor other metals with oxygen reduction catalytic activity by combining iron impurities in the carbon nanotubes, and is beneficial to improving the binding force of alloy nanoparticles and the carbon nanotube network macroscopic body so as to improve the catalytic activity and stability of a catalyst; and small-size metal alloy nanoparticles are obtained by a transient electric heating technology and are dispersed in the functionalized carbon nanotube network macroscopic body. The carbon nano tube network macroscopic body and the metal alloy nano particles have strong binding action force, excellent catalytic performance and strong stability, and also have excellent methanol poisoning resistance;
3) the metal alloy-carbon nano tube network macroscopic body composite material prepared by the invention is a network macroscopic body, is different from powder catalysts prepared by other technologies, does not need other additives, and can be directly used as an oxygen electrode for a metal air battery.
Drawings
Fig. 1 is a schematic flow chart of the preparation process of the metal alloy-carbon nanotube network macroscopic composite material in an exemplary embodiment of the present invention.
Fig. 2 is a schematic view of transient electrical heating in an exemplary embodiment of the invention.
Fig. 3 is a scanning transmission electron microscope image of a platinum-iron alloy/carbon nanotube high-angle annular dark field prepared in example 1 of the present invention.
FIG. 4 is an elemental distribution plot of X-ray energy dispersive line-sweep alloy nanoparticles Fe and Pt in example 1 of the present invention.
FIG. 5 is a graph of the oxygen reduction polarization of a Pt-Fe alloy/carbon nanotube network macroscopic body in example 1 of the present invention.
Fig. 6 is a schematic diagram of the stability and methanol poisoning resistance test results of the platinum-iron alloy/carbon nanotube network macroscopic body in example 1 of the present invention.
FIG. 7 is a graph of oxygen reduction polarization of a Pt-Fe alloy/carbon nanotube network macroscopic body in example 2 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
It is to be noted that the definitions of the terms mentioned in the description of the present invention are known to those skilled in the art. For example, some of the terms are defined as follows:
1. oxygen functional electrocatalytic electrode: an electrode for generating oxygen catalytic reaction comprises a catalyst, a carbon carrier and a porous electrode.
2. Floating catalytic chemical vapor deposition: the chemical vapor deposition method is characterized in that reactants and carrier gas are injected into a high-temperature tube furnace, so that the synthesis of the carbon nano tube is realized in one step and the carbon nano tube is assembled into fiber. In this method, the raw material is freely reacted in the carrier gas after injection, and a substrate for deposition is not required.
One aspect of an embodiment of the present invention provides a method for preparing a metal alloy-carbon nanotube network macroscopic body composite material, which includes:
(1) providing a carbon nanotube network macroscopic body, wherein the carbon nanotube network macroscopic body contains a simple substance of iron as a trace impurity;
(2) activating the carbon nano tube network macroscopic body;
(3) contacting the activated carbon nanotube network macroscopic body with a metal precursor solution to perform a displacement reaction on the iron simple substance and the metal precursor to generate a metal simple substance combined with the iron simple substance, wherein the metal simple substance has oxygen reduction catalytic activity, and then performing drying treatment;
(4) and (4) performing transient electric heating on the carbon nano tube network macroscopic body treated in the step (3) to obtain the metal alloy-carbon nano tube network macroscopic body composite material.
In some exemplary embodiments, the content of the iron in the carbon nanotube network macroscopic body is 1 to 10 wt%.
In some exemplary embodiments, the carbon nanotube network macroscopic body in step (1) is formed by using an Fe-based catalyst and is prepared by a chemical vapor deposition method or a floating catalyst chemical vapor deposition method.
Further, the form of the carbon nanotube network macroscopic body includes, but is not limited to, any one or a combination of two or more of a film, a fiber, an aerogel, a foam, and the like.
In some exemplary embodiments, the activation treatment in step (2) includes, but is not limited to, electrochemical anode activation, and may further include any one or a combination of two or more of oxygen plasma activation, acidification, and the like.
Further, the activation treatment time can be 1-20 min, and carbon nanotube networks with different activation degrees can be obtained.
In some exemplary embodiments, step (2) specifically includes: the activation treatment is carried out by using the carbon nano tube network macroscopic body as an anode, any one of a platinum sheet, a platinum wire, a platinum net, a graphite sheet and the like as a counter electrode, and using a mixed solution of strong base, ethanol and water as an electrolyte.
Further, the mass volume ratio of the strong base, water and ethanol in the mixed solution is 0.1-0.4 g: 1 ml: 1-20 ml.
Further, the strong base includes sodium hydroxide, but is not limited thereto.
In some preferred embodiments, the preparation method comprises: the activation treatment is carried out by adopting direct current and constant current, wherein the current intensity is 50-200 mA/cm2The activation treatment time is 1-20 min.
In some exemplary embodiments, step (3) specifically includes: and (3) soaking the activated carbon nano tube network macroscopic body in a metal precursor solution, and then drying.
Further, the metal contained in the metal precursor solution is another metal having oxygen reduction catalytic activity, including but not limited to any one or a combination of two or more of Co, Ni, Pt, Pb, Ir, Ag, Cu, Au, and the like.
Further, the metal precursor solution includes any one or a combination of two or more of aqueous solutions of chloride, sulfate, and nitrate of the contained metal, and for example, chloroplatinic acid, chloroauric acid, palladium chloride, chloroiridic acid, silver nitrate, cobalt chloride, and an aqueous solution of cobalt nitrate may be preferable, but not limited thereto.
In some preferred embodiments, the concentration of the metal precursor solution is 1-10 mmol/L.
In some preferred embodiments, the time for the immersion may be 10 to 60 min.
In some preferred embodiments, the drying process may be any one of atmospheric drying, freeze drying, supercritical drying, and the like, but is not limited thereto.
Further, the temperature of the drying treatment is 20-50 ℃.
In some exemplary embodiments, step (4) specifically includes: and (3) in a protective atmosphere, introducing current to the carbon nano tube network macroscopic body treated in the step (3), and performing transient electric heating to obtain the metal alloy-carbon nano tube network macroscopic body composite material.
Further, the energization conditions of the transient electric heating in the step (4) include a direct current constant potential, a direct current constant current and the like.
Further, the transient electric heating includes direct current constant potential heating or direct current constant current heating.
Further, the potential adopted by the direct current constant potential heating is 1-60V.
Further, the current density adopted by the direct current constant current heating is 0.1-2.5A/cm2。
In some preferred embodiments, the transient electric heating is powered on for 10-1000 ms.
In some preferred embodiments, the transient electrically heated gas atmosphere in step (4) is a protective atmosphere formed by a protective gas, and may be at least one of argon, nitrogen, and the like, but is not limited thereto.
In conclusion, the preparation method of the metal alloy-carbon nanotube network macroscopic body composite material provided by the invention has the advantages of low cost, simplicity, practicability and short time consumption, and the preparation process of electric heating alloying only needs less than one second.
The preparation method of the metal alloy-carbon nanotube network macroscopic body composite material provided by the invention utilizes a functional treatment means to anchor other metals with oxygen reduction catalytic activity by combining iron impurities in the carbon nanotubes, and is beneficial to improving the binding force of alloy nanoparticles and the carbon nanotube network macroscopic body so as to improve the catalytic activity and stability of a catalyst; and small-size metal alloy nanoparticles are obtained by a transient electric heating technology and are dispersed in the functionalized carbon nanotube network macroscopic body. The carbon nano tube network macroscopic body and the metal alloy nano particles have strong binding action force, excellent catalytic performance and strong stability, and simultaneously have excellent methanol poisoning resistance.
Another aspect of an embodiment of the present invention provides a metal alloy-carbon nanotube network macroscopic body composite material prepared by the foregoing method.
Another aspect of the embodiments of the present invention provides a metal alloy-carbon nanotube network macroscopic body composite material, which includes a carbon nanotube network macroscopic body and metal alloy nanoparticles, wherein the metal alloy nanoparticles are uniformly loaded in a carbon nanotube network of the carbon nanotube network macroscopic body, and the metal alloy nanoparticles include a Fe simple substance and a metal simple substance having an oxygen reduction catalytic activity.
Further, the elementary substance Fe is distributed in at least part of the carbon nanotubes for constituting the macroscopic body of the carbon nanotube network.
Further, the content of the Fe simple substance in the carbon nano tube network macroscopic body is more than 1 wt% and less than 10 wt%.
Further, the metal alloy nanoparticles have a size greater than 0 and less than 5 nm.
Further, the content of the metal alloy nanoparticles in the metal alloy-carbon nanotube network macroscopic composite material is 1-10 wt%.
Further, the mass ratio of the Fe elementary substance to the metal elementary substance with oxygen reduction catalytic activity in the metal alloy nanoparticles is 1: 1-100: 1.
further, the elemental metal having the oxygen reduction catalytic activity includes any one or a combination of two or more of Co, Ni, Pt, Pb, Ir, Ag, Cu, Au, and the like, but is not limited thereto.
Further, the specific surface area of the carbon nano tube network macroscopic body is 100-300 m2g-1。
Furthermore, the oxygen reduction catalytic performance, the stability and the methanol poisoning resistance of the metal alloy-carbon nanotube network macroscopic body composite material are superior to those of a commercial Pt/C catalyst.
In another aspect of the embodiment of the present invention, there is also provided an application of any one of the foregoing metal alloy-carbon nanotube network macroscopic body composite materials in preparation of an oxygen electrode or a metal-air battery.
Accordingly, another aspect of an embodiment of the present invention also provides an oxygen electrode comprising any one of the foregoing metal alloy-carbon nanotube network macroscopic body composite materials.
Further, the oxygen electrode may be an oxygen reduction electrocatalytic electrode or an oxygen reduction and oxygen evolution bifunctional oxygen electrode.
Accordingly, another aspect of an embodiment of the present invention also provides a metal-air battery, which includes any one of the foregoing metal alloy-carbon nanotube network macroscopic body composite materials or oxygen electrodes.
The metal alloy-carbon nano tube network macroscopic body composite material prepared by the invention is a network macroscopic body, is different from powder catalysts prepared by other technologies, does not need other additives, and can be directly used as an oxygen electrode for a metal air battery.
Of course, the metal alloy-carbon nanotube network macroscopic body composite material can also be directly used for preparing the oxygen reduction catalyst.
Accordingly, another aspect of an embodiment of the present invention also provides an oxygen reduction catalyst comprising any one of the foregoing metal alloy-carbon nanotube network macroscopic body composite materials.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
The preparation process of the metal alloy-carbon nanotube network macroscopic body composite material provided by the embodiment is shown in fig. 1, and includes the following steps:
step 1, providing a carbon nano tube network macroscopic body prepared by a floating chemical vapor deposition method, wherein the preparation process comprises the following steps: the FCCVD tube furnace apparatus was heated to 1300 ℃ and an absolute ethanol solution containing 2 wt.% ferrocene and 0.4 wt.% thiophene was injected with a syringe pump at a rate of 20mL h-1The carrier gas is Ar/H2Ar flow rate of 2200sccm, H for mixed gas2The flow rate is 2000sccm, the original CNT aerogel is collected by a roller after floating out from the tail, and is further compressed by a roller shaft after being sprayed with ethanol for infiltration to obtain a carbon nanotube network macroscopic body containing 5% of iron simple substance impurities by mass fraction, and then is subjected to electrochemical activation treatment, wherein the electrochemical activation treatment comprises the following steps: the carbon nano tube network macroscopic body is taken as an anode, a platinum sheet with the same area is taken as a counter electrode, a solution of 0.4g of sodium hydroxide dissolved in 1mL of water and 20mL of ethanol is taken as an electrolyte, and the direct current constant current is 50mA/cm2Treating for 10 min;
step 3, drying the carbon nano tube network macroscopic body treated in the step 2 at room temperature of 25 ℃;
and 4, referring to fig. 2, connecting two ends of the carbon nano tube network macroscopic body treated in the step 3 with copper foils, placing the macroscopic body in a quartz tube saturated by argon, and applying direct current constant current (current density: 0.2A/cm) to the two ends2) The power is switched on for 250ms, the temperature can reach 1400K instantly, the formation of the platinum-iron alloy is promoted by the process of instant temperature rise-temperature reduction caused by the joule heat effect, the functionalized carbon nanotube network macroscopic body provides a load site for the nano alloy, and finally the 6.8 mu g cm-shaped platinum-iron alloy with high catalytic activity, stability and methanol poisoning resistance is formed-2The platinum-iron alloy-carbon nanotube network macroscopic body composite material with low platinum content.
FIG. 3 shows the micro-morphology of a typical Pt-Fe alloy/carbon nanotube network macroscopic composite material product obtained in this example, which includes small size: (<5nm) platinum-iron alloy nano particles, and the alloy nano particles are uniformly loaded in the network of the carbon nanotube bundles. The elemental analysis structure of the product is shown in fig. 4, where Fe and Pt elements are uniformly distributed in the line-swept area of the alloy nanoparticles. Further, referring to FIGS. 5 and 6, the product also showed excellent catalytic performance for oxygen reduction, with specific activity of oxygen reduction mass at 0.85V (relative reversible hydrogen electrode potential) of 330mA gPt -1And the stability and the methanol poisoning resistance are kept for a long time.
Example 2
Step 1, providing a carbon nano tube network macroscopic body prepared by a floating chemical vapor deposition method, wherein the preparation process comprises the following steps: the FCCVD tube furnace apparatus was heated to 1300 ℃ and an absolute ethanol solution containing 2 wt.% ferrocene and 0.4 wt.% thiophene was injected with a syringe pump at a rate of 20mL h-1The carrier gas is Ar/H2Ar flow rate of 2200sccm, H for mixed gas2The flow rate is 2000sccm, the original CNT aerogel is collected by a roller after floating out from the tail, and is further compressed by a roller shaft after being sprayed and soaked with ethanol to obtain a carbon nanotube network macroscopic body containing 1 wt.% of iron simple substance impurities, and then is subjected to electrochemical activation treatment, wherein the electrochemical activation treatment comprises the following steps: the carbon nano tube network macroscopic body is taken as an anode, a platinum sheet with the same area is taken as a counter electrode, a solution of 0.2g of sodium hydroxide dissolved in 1mL of water and 20mL of ethanol is taken as an electrolyte, and the direct current constant current is 100mA/cm2Treating for 1 min;
step 3, drying the carbon nano tube network macroscopic body treated in the step 2 at room temperature of 20 ℃;
and 4, referring to fig. 2, connecting two ends of the carbon nano tube network macroscopic body processed in the step 3 with copper foils, placing the carbon nano tube network macroscopic body in a quartz tube saturated by argon, applying direct current constant potential of 60V to electrify for 250ms at two ends, and promoting the formation of a platinum-iron alloy by the instant temperature rise-temperature reduction process caused by the joule heat effect, wherein the functionalized carbon nano tube network macroscopic body provides a load site for the nano alloy to finally form the platinum-iron alloy-carbon nano tube network macroscopic body composite material, and the specific activity of the oxygen reduction quality at 0.85V (relative reversible hydrogen electrode potential) is about 190mA g as shown in fig. 7pt -1。
Example 3
Step 1, providing a carbon nano tube network macroscopic body prepared by a floating chemical vapor deposition method, wherein the preparation process comprises the following steps: the FCCVD tube furnace apparatus was heated to 1300 ℃ and an absolute ethanol solution containing 2 wt.% ferrocene and 0.4 wt.% thiophene was injected with a syringe pump at a rate of 20mL h-1The carrier gas is Ar/H2Ar flow rate of 2200sccm, H for mixed gas2The flow rate is 2000sccm, the original CNT aerogel is collected by a roller after being floated out from the tail part, is further compressed by a roller shaft after being sprayed and soaked by ethanol to obtain a carbon nanotube network macroscopic body containing 10 wt.% of iron simple substance impurities, and is subjected to electrochemical activation treatment, wherein the electrochemical activation treatment comprises the following steps: the carbon nano tube network macroscopic body is used as an anode, a platinum sheet with the same area is used as a counter electrode, a solution of 0.1g of sodium hydroxide dissolved in 1mL of water and 20mL of ethanol is used as an electrolyte, and the direct current constant current is 200mA/cm2Treating for 20 min;
step 3, drying the carbon nano tube network macroscopic body treated in the step 2 at room temperature of 50 ℃;
and 4, referring to fig. 2, connecting two ends of the carbon nano tube network macroscopic body treated in the step 3 with copper foils, placing the carbon nano tube network macroscopic body in a quartz tube saturated by argon, applying direct current constant potential 30V to electrify the two ends for 250ms, and promoting the formation of the palladium-iron alloy by the instant heating-cooling process caused by the joule heating effect, wherein the functionalized carbon nano tube network macroscopic body provides a load site for the nano alloy, and finally the palladium-iron alloy-carbon nano tube network macroscopic body composite material is formed.
Example 4
This embodiment is substantially the same as embodiment 1 except that: step 2, adopting chloroauric acid aqueous solution as metal precursor solution, and step 4, applying direct current constant current (current density: 0.1A/cm) at two ends2) Power is applied for 1000 ms.
Example 5
This embodiment is substantially the same as embodiment 1 except that: the metal precursor solution in step 2 is chloro-iridic acid aqueous solution, and in step 4, direct current constant current (current density: 2.5A/cm) is applied to two ends2) Power is applied for 10 ms.
Example 6
This embodiment is substantially the same as embodiment 2 except that: the two ends are electrified for 1000ms by applying a direct current constant potential 1V.
The performance of the metal alloy-carbon nanotube network macroscopic composite materials obtained in examples 4-6 was tested to be substantially the same as that of example 1.
Through the examples 1-6, it can be found that the invention utilizes the functionalization treatment means to anchor other metals with oxygen reduction catalytic activity in combination with iron impurities in the carbon nanotubes, and through the technology of transient electric heating, the bonding force between the obtained carbon nanotube network macroscopic body and the metal alloy nanoparticles is strong, the catalytic performance is excellent and the stability is strong, and the invention also has excellent methanol poisoning resistance, and can be directly used as an oxygen electrode for a metal air battery.
In addition, the inventors of the present invention also conducted experiments using other raw materials and conditions listed in the present specification, etc., in the manner of examples 1 to 6, and also obtained a metal alloy-carbon nanotube network macroscopic composite material having excellent catalytic performance and strong stability, and also having excellent methanol poisoning resistance.
It should be understood that the above describes only some embodiments of the present invention and that various other changes and modifications may be affected therein by one of ordinary skill in the related art without departing from the scope or spirit of the invention.
Claims (31)
1. A method for preparing a metal alloy-carbon nanotube network macroscopic body composite material is characterized by comprising the following steps:
(1) providing a carbon nanotube network macroscopic body, wherein the carbon nanotube network macroscopic body contains a simple substance of iron as a trace impurity;
(2) activating the carbon nano tube network macroscopic body;
(3) contacting the activated carbon nanotube network macroscopic body with a metal precursor solution to perform a displacement reaction on the iron simple substance and the metal precursor to generate a metal simple substance combined with the iron simple substance, wherein the metal simple substance has oxygen reduction catalytic activity, and then performing drying treatment;
(4) and (4) performing transient electric heating on the carbon nano tube network macroscopic body treated in the step (3) to obtain the metal alloy-carbon nano tube network macroscopic body composite material.
2. The method of claim 1, wherein: the carbon nano tube network macroscopic body in the step (1) is prepared by adopting an Fe-based catalyst through a chemical vapor deposition method or a floating catalytic chemical vapor deposition method;
and/or the content of the iron simple substance in the carbon nano tube network macroscopic body is 1-10 wt%.
3. The method of claim 1, wherein: the form of the carbon nano tube network macroscopic body in the step (1) comprises any one or the combination of more than two of films, fibers, aerogels and foams.
4. The method of claim 1, wherein: the activating treatment mode in the step (2) comprises any one or combination of more than two of electrochemical anode activation, oxygen plasma activation and acidification.
5. The method of claim 4, wherein: the activation treatment time is 1-20 min.
6. The method according to claim 4, wherein the step (2) specifically comprises: and (3) taking the carbon nano tube network macroscopic body as an anode, opposite to a counter electrode, and taking a mixed solution of strong base, ethanol and water as an electrolyte to carry out the activation treatment.
7. The method of claim 6, wherein: the counter electrode comprises a platinum sheet, a platinum wire, a platinum net or a graphite sheet.
8. The method of claim 6, wherein: the mass volume ratio of strong base, water and ethanol contained in the mixed solution is 0.1-0.4 g: 1 ml: 1-20 ml; and/or, the strong base comprises sodium hydroxide.
9. The production method according to claim 6, characterized by comprising: the activation treatment is carried out by adopting direct current and constant current, wherein the current intensity is 50-200 mA/cm2The activation treatment time is 1-20 min.
10. The method according to claim 1, wherein the step (3) specifically comprises: and (3) soaking the activated carbon nano tube network macroscopic body in a metal precursor solution, and then drying.
11. The method of manufacturing according to claim 10, wherein: the metal element contained in the metal precursor solution comprises any one or the combination of more than two of Co, Ni, Pt, Pb, Ir, Ag, Cu and Au.
12. The method of claim 11, wherein: the metal precursor solution comprises any one or the combination of more than two of the aqueous solutions of chloride, sulfate and nitrate of the contained metal.
13. The method of manufacturing according to claim 12, wherein: the metal precursor solution comprises one or the combination of more than two of chloroplatinic acid, chloroauric acid, palladium chloride, chloroiridic acid, silver nitrate, cobalt chloride and cobalt nitrate aqueous solution.
14. The method of manufacturing according to claim 10, wherein: the concentration of the metal precursor solution is 1-10 mmol/L.
15. The method of manufacturing according to claim 10, wherein: the dipping time is 10-60 min.
16. The method of manufacturing according to claim 10, wherein: the drying treatment mode comprises any one of normal pressure drying, freeze drying and supercritical drying.
17. The method of claim 8, wherein: the temperature of the drying treatment is 20-50 ℃.
18. The method according to claim 1, wherein the step (4) specifically comprises: and (3) in a protective atmosphere, introducing current to the carbon nano tube network macroscopic body treated in the step (3), and performing transient electric heating to obtain the metal alloy-carbon nano tube network macroscopic body composite material.
19. The method of claim 18, wherein: the transient electric heating comprises direct current constant potential heating or direct current constant current heating.
20. The method of claim 19, wherein: the potential adopted by the direct current constant potential heating is 1-60V.
21. The method of claim 19, wherein: the current density adopted by the direct current constant current heating is 0.1-2.5A/cm2。
22. The method of claim 19, wherein: the power-on time of the transient electric heating is 10-1000 ms.
23. The method of claim 18, wherein: the protective atmosphere comprises an argon and/or nitrogen atmosphere.
24. A metal alloy-carbon nanotube network macroscopic composite prepared by the method of any one of claims 1-23.
25. The metal alloy-carbon nanotube network macroscopic body composite material is characterized by comprising a carbon nanotube network macroscopic body and metal alloy nanoparticles, wherein the metal alloy nanoparticles are uniformly loaded in a carbon nanotube network of the carbon nanotube network macroscopic body, and the metal alloy nanoparticles comprise a Fe simple substance and a metal simple substance with oxygen reduction catalytic activity.
26. The metal alloy-carbon nanotube network macroscopic composite of claim 25, wherein: the Fe simple substance is distributed in at least part of the carbon nanotubes for constituting the carbon nanotube network macroscopic body; preferably, the content of the Fe element in the carbon nanotube network macroscopic body is more than 1 wt% and less than 10 wt%.
27. The metal alloy-carbon nanotube network macroscopic composite of claim 25, wherein: the metal alloy nanoparticles have a size greater than 0 and less than 5 nm; and/or the content of metal alloy nanoparticles in the metal alloy-carbon nanotube network macroscopic body composite material is 1-10 wt%;
and/or the mass ratio of the Fe elementary substance to the metal elementary substance with oxygen reduction catalytic activity is 1: 1-100: 1;
and/or the metal simple substance with the oxygen reduction catalytic activity comprises any one or the combination of more than two of Co, Ni, Pt, Pb, Ir, Ag, Cu and Au;
and/or the specific surface area of the carbon nano tube network macroscopic body is 100-300 m2g-1。
28. Use of the metal alloy-carbon nanotube network macroscopic composite of any one of claims 24 to 27 in the preparation of an oxygen electrode or a metal air battery.
29. An oxygen electrode comprising the metal alloy-carbon nanotube network macroscopic composite material of any one of claims 24 to 27.
30. The oxygen electrode of claim 29, wherein: the oxygen electrode comprises an oxygen reduction electrocatalysis electrode or an oxygen reduction and oxygen precipitation dual-function oxygen electrode.
31. A metal-air battery characterized by comprising the metal alloy-carbon nanotube network macroscopic composite material of any one of claims 24 to 27 or the oxygen electrode of any one of claims 29 to 30.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578222A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Nanocomposite synthesis device based on instantaneous high-temperature Joule heating method, preparation method and application |
| CN116535227A (en) * | 2023-07-05 | 2023-08-04 | 西南交通大学 | Preparation method of carbon fiber in-situ generation nano silver enhanced pantograph carbon slide plate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102983380A (en) * | 2012-11-07 | 2013-03-20 | 华中科技大学 | Lithium air battery based on three-dimensional carbon nanotube structure and preparation method thereof |
| CN105810952A (en) * | 2014-12-30 | 2016-07-27 | 北京有色金属研究总院 | Air positive electrode composite carrier material for lithium air batteries and preparation method thereof |
| JP2017010914A (en) * | 2015-06-26 | 2017-01-12 | 日本碍子株式会社 | Air electrode, metal-air battery, air electrode material, and method for producing air electrode material |
| CN108543545A (en) * | 2018-04-26 | 2018-09-18 | 大连理工大学 | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications |
-
2019
- 2019-04-04 CN CN201910269590.0A patent/CN111785979B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102983380A (en) * | 2012-11-07 | 2013-03-20 | 华中科技大学 | Lithium air battery based on three-dimensional carbon nanotube structure and preparation method thereof |
| CN105810952A (en) * | 2014-12-30 | 2016-07-27 | 北京有色金属研究总院 | Air positive electrode composite carrier material for lithium air batteries and preparation method thereof |
| JP2017010914A (en) * | 2015-06-26 | 2017-01-12 | 日本碍子株式会社 | Air electrode, metal-air battery, air electrode material, and method for producing air electrode material |
| CN108543545A (en) * | 2018-04-26 | 2018-09-18 | 大连理工大学 | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578222A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Nanocomposite synthesis device based on instantaneous high-temperature Joule heating method, preparation method and application |
| CN116535227A (en) * | 2023-07-05 | 2023-08-04 | 西南交通大学 | Preparation method of carbon fiber in-situ generation nano silver enhanced pantograph carbon slide plate |
| CN116535227B (en) * | 2023-07-05 | 2023-10-10 | 西南交通大学 | Preparation method of carbon fiber in-situ generation nano silver enhanced pantograph carbon slide plate |
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