CN115207378A - Polypyrrole nanotube electrocatalyst and preparation method and application thereof - Google Patents
Polypyrrole nanotube electrocatalyst and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- 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
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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Abstract
The invention discloses a polypyrrole nanotube electrocatalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: dispersing an oxide of a transition metal or a soluble salt of the transition metal in water, and stirring until the transition metal is completely dissolved to obtain a first solution; adding methyl orange into the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second solution; adding pyrrole monomer into the second solution, stirring and polymerizing to obtain a polypyrrole nanotube wrapped with a transition metal oxide or a transition metal salt; and calcining the polypyrrole nanotube coated with the transition metal oxide or the transition metal salt in a reducing atmosphere to obtain the polypyrrole nanotube electrocatalyst coated with the transition metal simple substance. The method has reasonable design and convenient operation, and obtains the electrocatalyst which has good catalytic performance, high specific surface area and porosity and a gas channel with good electronic conductivity and mechanical strength.
Description
Technical Field
The invention belongs to the field of battery electrode materials, and relates to a polypyrrole nanotube electrocatalyst, a preparation method and application thereof.
Background
The battery as a green and sustainable energy technology conforms to the development requirement of the current society. Among them, the metal-air battery has attracted attention because of its advantages of high theoretical energy density, good safety, low cost, environmental protection, etc. The choice of electrocatalyst electrode materials for metal-air batteries is critical to battery performance. The anode electrocatalyst material of the metal-air battery needs to realize the dual functions of a gas channel and a catalyst carrier, and needs to have higher electronic conductivity, high specific surface area and porosity and higher mechanical strength. Currently, the commonly used electrocatalysts are precious metal catalysts represented by Pt, ir and the like, but the precious metal resources are rare, the cost is high, and the industrial application is difficult. The transition metal compound has the advantages of rich crust reserve, low price, strong alkali resistance, strong oxidation resistance and the like, and becomes a research hotspot as a high-efficiency non-noble metal catalyst. However, the catalyst has the defects of poor conductivity, low catalytic active site exposure rate and the like, so that the catalytic performance is not ideal.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a polypyrrole nanotube electrocatalyst, a preparation method and application thereof. Thus obtaining the electrocatalyst with good catalytic performance, high specific surface area and porosity and gas channels with good electronic conductivity and mechanical strength.
The invention is realized by the following technical scheme:
a preparation method of a polypyrrole nanotube electrocatalyst comprises the following steps:
s1: dispersing an oxide of a transition metal or a soluble salt of the transition metal in water, and stirring until the transition metal is completely dissolved to obtain a first solution;
s2: adding methyl orange into the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second solution;
s3: adding pyrrole monomer into the second solution, stirring and polymerizing to obtain a polypyrrole nanotube wrapped with a transition metal oxide or a transition metal salt;
s4: and calcining the polypyrrole nanotube coated with the transition metal oxide or the transition metal salt in a reducing atmosphere to obtain the polypyrrole nanotube electrocatalyst coated with the transition metal simple substance.
Preferably, the oxide of the transition metal is CoO, cuO or Fe 2 O 3 And NiO.
Preferably, the soluble salt of the transition metal is CoCl 2 、CuCl 2 、FeCl 3 And NiCl 2 Any one of them.
Preferably, the pyrrole monomer is purified by adopting a reduced pressure distillation mode before being added into a reaction system; the temperature of the reduced pressure distillation is 80-100 ℃, and the pressure is 0.08MPa.
Preferably, the reducing atmosphere comprises a hydrogen atmosphere or a carbon monoxide atmosphere.
Preferably, the temperature of the calcination is 400 to 600 ℃.
Preferably, the molar ratio of the pyrrole monomer to the transition metal in the oxide or soluble salt of the transition metal is 1 (0.5-2.5).
Preferably, the concentration range of the methyl orange is 3 mmol/L-5 mmol/L, and the ratio of the pyrrole monomer to the ferric chloride is 1 (0.5-2.5).
The polypyrrole nanotube electrocatalyst prepared by the method has the specific surface area of 600-820 m 2 (ii)/g; the power density of the polypyrrole nanotube electrocatalyst is 70-154 mW cm -2 。
The polypyrrole nanotube electrocatalyst prepared by the preparation method is applied to a metal-air battery.
Compared with the prior art, the invention has the following beneficial technical effects:
a polypyrrole nanotube electrocatalyst is prepared by adopting methyl orange as a soft template agent, ferric chloride as an oxidant and pyrrole monomers in a polymerization process, wherein a tubular structure can be used as a gas channel, the catalytic efficiency of a metal-air battery electrocatalyst is improved, meanwhile, an oxide of a transition metal or a soluble salt of the transition metal is added into a reaction system, in the synthesis process of the polypyrrole nanotube, the oxide of the transition metal or the soluble salt of the transition metal is wrapped in the polypyrrole nanotube in situ, and meanwhile, the polypyrrole nanotube wrapped with a transition metal simple substance is obtained by calcining in a reducing atmosphere, and the polypyrrole nanotube forms a more stable nitrogen-carbon (N-C) structure in the calcining process, so that a (metal-nitrogen-carbon) M-N-C type polypyrrole nanotube electrocatalyst with good performance is formed. The method has reasonable design and convenient operation, and obtains the electrocatalyst which has good catalytic performance, high specific surface area and porosity and a gas channel with good electronic conductivity and mechanical strength.
Furthermore, the pyrrole monomer is purified by adopting a reduced pressure distillation mode before the polymerization reaction, so that the purity of the synthesized polypyrrole nanotube can be effectively reduced.
Furthermore, the calcining temperature is 400-600 ℃, on one hand, the structural stability of the polypyrrole nanotube is ensured, and on the other hand, the oxide of the transition metal or the solubility of the transition metal can be effectively reduced to the transition metal simple substance in the reducing atmosphere.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic flow diagram of a method for preparing a polypyrrole nanotube electrocatalyst in the present invention;
FIG. 2 is an SEM photograph of the polypyrrole nanotube electrocatalyst under different magnifications obtained in example 3 of the invention.
FIG. 3 is a TEM image of the polypyrrole nanotube electrocatalyst prepared in example 3 of the present invention.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," "including," "having," or similar terms, shall mean "consisting of 8230; \8230, composition" and "consisting essentially of 8230; \8230, composition" such as "A comprises a" shall mean "A comprises a and the other" and "A comprises a only".
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
Researches show that the direct use of non-noble metals as electrocatalysts has low catalytic efficiency, and at present, the catalytic efficiency is mainly improved by doping, and the electrocatalysts mainly comprise transition metal heteroatom co-doped carbon and heteroatom doping of N, B, S, O, P and the like. Currently, in non-metal doping modification, nitrogen atoms can be doped to the edge or inside of the carbon structure due to the similar size of nitrogen and carbon atoms, resulting in corresponding active sites. Because nitrogen doping is easier to realize than doping with other heteroatoms and can generate a plurality of corresponding active sites, the transition metal and nitrogen-doped carbon catalyst becomes a catalyst which has more practical value and is more hopeful to replace noble metal, and is called as a transition metal and nitrogen-modified carbon catalyst, namely M-N-C catalyst for short. Such heteroatom-modified carbon catalytic materials are considered potential replacements for noble metal catalysts due to their cheapness, stability, and good electrical conductivity. However, the M-N-C catalyst reported in the current research has the disadvantages of complex synthetic route and undesirable catalytic efficiency.
The polypyrrole is selected as a base material, has an N-C structure molecular base, and can effectively improve the electronic conductivity of the catalyst to achieve high catalytic efficiency. Meanwhile, in the polymerization process of the polypyrrole, various shapes such as a round tube shape, a square tube shape and the like can be realized through the induction of a template agent, and the natural pore channel structures can be used as gas channels to improve the catalytic efficiency of the metal-air battery electrocatalyst. And the pore size of the polypyrrole tube can be adjusted by controlling the reaction conditions, so that the appearance and the tube diameter of the polypyrrole tube can be adjusted and controlled according to actual application conditions by taking the polypyrrole tube as a load carrier of the transition metal, and the load capacity and the gas flux of the catalyst can be adjusted and controlled. The polypyrrole is used as a conductive polymer, has the advantages of high electronic conductivity and high mechanical strength, and can be used for preparing the polypyrrole nanotube with a hollow structure by controlling reaction conditions, so that the polypyrrole nanotube with a high specific surface area can be prepared. Meanwhile, the polypyrrole has corrosion resistance. Therefore, the polypyrrole nanotube is an electrode electrocatalyst material with various excellent performances, and has good corrosion resistance.
In order to construct the polypyrrole nanotube electrocatalyst with excellent performance, the preparation method is shown in fig. 1, and specifically comprises the following steps:
s1: dispersing an oxide of a transition metal or a soluble salt of the transition metal in water, and stirring until the transition metal is completely dissolved to obtain a first solution;
wherein the transition metal oxide comprises CoO, cuO, and Fe 2 O 3 And NiO. Soluble salts of transition metals include CoCl 2 、CuCl 2 、FeCl 3 And NiCl 2 Any one of them. The molar ratio of the pyrrole monomer to the transition metal in the oxide or soluble salt of the transition metal is 1 (0.5-2.5).
S2: adding methyl orange into the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second solution; wherein the concentration range of the methyl orange is 3 mmol/L-5 mmol/L.
S3: adding pyrrole monomer into the second solution, stirring and polymerizing to obtain a polypyrrole nanotube wrapped with a transition metal oxide or a transition metal salt; wherein the mass ratio of the pyrrole monomer to the ferric chloride is 1 (0.5-2.5), and the pyrrole monomer is purified by adopting a reduced pressure distillation mode before the polymerization reaction; the temperature of the reduced pressure distillation is 80-100 ℃, and the pressure is 0.08MPa.
S4: and calcining the polypyrrole nanotube coated with the transition metal oxide or the transition metal salt in a reducing atmosphere to obtain the polypyrrole nanotube electrocatalyst coated with the transition metal simple substance.
Wherein the reducing atmosphere comprises a hydrogen atmosphere or a carbon monoxide atmosphere; the calcining temperature is 400-600 ℃.
The polypyrrole nanotube electrocatalyst prepared by the method has the tube diameter of 80-200nm and the specific surface area of 600-820 m 2 (ii)/g; the power density is 70-154 mW cm -2 。
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Instrumentation conventional in the art is used in the following examples. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
The pyrrole monomer is purified by a reduced pressure distillation method, wherein the temperature of the reduced pressure distillation is 80 ℃, and the pressure is 0.08MPa. 0.55g of CuCl was taken 2 Dispersing in 300mL deionized water, and stirring for 30min at normal temperature to completely dissolve. 300mg of methyl orange is dissolved in 300mL of the solution, the solution is stirred for 5h at normal temperature until the solution becomes clear pink, then 2.22g of ferric chloride hexahydrate is slowly added, and the solution immediately appears dark red flocculent precipitate. Rapidly stirring for 50min, adding 1.1g pyrrole monomer, observing the solution to turn into black green, and polymerizing at room temperature (25 deg.C) for 24 hr by in-situ polymerization method to obtain a product coated with CuCl 2 The polypyrrole nanotube of (1). Suction filtering, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, removing the template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, drying until the pH value is neutral. Wrapping the obtained product with CuCl 2 The polypyrrole nanotube is placed in a hydrogen atmosphere and calcined at 400 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Cu simple substance.
The polypyrrole nanotube electrocatalyst wrapped with the Cu simple substance prepared by the embodiment has the tube diameter of 80nm and the specific surface area of 600m 2 G, power density of 70mW cm -2 。
Example 2
The pyrrole monomer is purified by a reduced pressure distillation method, wherein the temperature of the reduced pressure distillation is 90 ℃, and the pressure is 0.08MPa. 0.55g of CuCl was taken 2 Dispersing in 490mL deionized water, stirring at room temperature for 30min to dissolve completely. Dissolving 300mg methyl orange in 300mL of the above solution, stirring at normal temperature for 5h until the solution turns into clear pink, slowly adding 2.22g ferric trichloride hexahydrate, and making the solution immediately appear dark red flocculent precipitateAnd (4) precipitating. Rapidly stirring for 50min, adding 1.1g pyrrole monomer, observing the solution to turn into black green, and polymerizing at room temperature (25 deg.C) for 24 hr by in-situ polymerization method to obtain CuCl-coated product 2 The polypyrrole nanotube of (1). Suction filtering, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, removing the template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, drying until the pH value is neutral. Wrapping the obtained product with CuCl 2 The polypyrrole nanotube is placed in a hydrogen atmosphere and calcined at the temperature of 440 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Cu simple substance.
The polypyrrole nanotube electrocatalyst wrapped with the Cu simple substance prepared by the embodiment has the tube diameter of 100nm and the specific surface area of 700m 2 G, power density of 78mW cm -2 。
Example 3
The pyrrole monomer is purified by a reduced pressure distillation method, wherein the temperature of the reduced pressure distillation is 100 ℃, and the pressure is 0.08MPa. 0.55g of CuCl was taken 2 Dispersing in 490mL deionized water, stirring for 30min at normal temperature to completely dissolve. 300mg of methyl orange is dissolved in 300mL of the solution, the solution is stirred for 5h at normal temperature until the solution becomes clear peach-red, then 6.65g of ferric chloride hexahydrate is slowly added, and the solution immediately appears dark red flocculent precipitate. Rapidly stirring for 50min, adding 1.1g pyrrole monomer, observing the solution to turn into black green, and polymerizing at room temperature (25 deg.C) for 24 hr by in-situ polymerization method to obtain CuCl-coated product 2 The polypyrrole nanotube of (1). Suction filtering, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, removing the template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, drying until the pH value is neutral. Wrapping the obtained product with CuCl 2 The polypyrrole nanotube is placed in a hydrogen atmosphere and calcined at 550 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Cu simple substance.
The polypyrrole nanotube electrocatalyst wrapped with the Cu simple substance prepared by the embodiment has the tube diameter of 120nm and the specific surface area of 720m 2 G, power density of 80mW cm -2 。
The SEM picture of the polypyrrole nanotube coated with the Cu simple substance prepared by the invention is shown in figure 2, the TEM picture is shown in figure 3, and the graph shows that the polypyrrole nanotube is about 80-200nm, has a hollow tubular structure and is internally coated with the transition metal simple substance.
Example 4
The pyrrole monomer is purified by a reduced pressure distillation method, wherein the temperature of the reduced pressure distillation is 95 ℃, and the pressure is 0.08MPa. 1.65g of CoCl was taken 2 Dispersing in 490mL deionized water, stirring for 30min at normal temperature to completely dissolve. 300mg of methyl orange is dissolved in 300mL of the solution, the solution is stirred for 5h at normal temperature until the solution becomes clear peach-red, then 6.65g of ferric chloride hexahydrate is slowly added, and the solution immediately appears dark red flocculent precipitate. Rapidly stirring for 50min, adding 1.1g pyrrole monomer, observing the solution to turn into black green, and polymerizing at room temperature (25 deg.C) for 24 hr by in-situ polymerization method to obtain a coated CoCl 2 The polypyrrole nanotube of (1). Suction filtering, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, removing the template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, drying until the pH value is neutral. The obtained product after drying is wrapped with CoCl 2 The polypyrrole nanotube is placed in a hydrogen atmosphere and calcined at the temperature of 450 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Co metal simple substance.
The diameter of the Co-coated polypyrrole nanotube electrocatalyst prepared by the embodiment is 140nm, and the specific surface area is 750m 2 G, power density of 90mW cm -2 。
Example 5
The pyrrole monomer is purified by a reduced pressure distillation method, wherein the temperature of the reduced pressure distillation is 85 ℃, and the pressure is 0.08MPa. 1.65g of CoO was dispersed in 490mL of deionized water and stirred at room temperature for 30min to dissolve completely. 300mg of methyl orange is dissolved in 300mL of the solution, the solution is stirred for 5 hours at normal temperature until the solution becomes clear pink, then 6.65g of ferric chloride hexahydrate is slowly added, and the solution immediately appears dark red flocculent precipitate. Rapidly stirring for 50min, adding 1.1g pyrrole monomer, observing the solution to turn into black green, and polymerizing at room temperature (25 deg.C) for 24h by in-situ polymerization method to obtain CoO-coated polypyrrole nano particlesA tube. Suction filtering, repeatedly washing the product with deionized water and absolute ethyl alcohol, removing template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, drying until the pH value is neutral. And (3) placing the polypyrrole nanotube wrapped with CoO obtained after drying in a hydrogen atmosphere, and calcining at 470 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Co simple substance.
The diameter of the Co-coated polypyrrole nanotube electrocatalyst prepared by the embodiment is 160nm, and the specific surface area is 780m 2 G, power density of 110mW cm -2 。
Example 6
The preparation method of the polypyrrole nanotube electrocatalyst is characterized by comprising the following steps of:
s1: dispersing CoO in water, and stirring until the CoO is completely dissolved to obtain a first solution;
s2: adding 3mmol/L methyl orange into the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second solution;
s3: adding pyrrole monomer into the second solution, wherein the mass ratio of the pyrrole monomer to ferric chloride is 1; stirring to perform in-situ polymerization reaction to obtain a polypyrrole nanotube wrapped with CoO;
s4: and (3) placing the polypyrrole nanotube coated with the CoO in a carbon monoxide atmosphere, and calcining at 400 ℃ to obtain the polypyrrole nanotube electrocatalyst coated with the Co simple substance.
The diameter of the Co-coated polypyrrole nanotube electrocatalyst prepared by the embodiment is 180nm, and the specific surface area is 800m 2 (g) power density of 115mW cm -2 。
Example 7
A preparation method of a polypyrrole nanotube electrocatalyst is characterized by comprising the following steps:
s1: dispersing CuO in water, and stirring until the CuO is completely dissolved to obtain a first solution;
s2: adding 4mmol/L methyl orange into the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second solution;
s3: adding pyrrole monomer into the second solution, wherein the mass ratio of the pyrrole monomer to the ferric chloride is 1; stirring to perform in-situ polymerization reaction to obtain a polypyrrole nanotube wrapped with CuO;
s4: and (3) placing the polypyrrole nanotube coated with CuO in a carbon monoxide atmosphere, and calcining at 500 ℃ to obtain the polypyrrole nanotube electrocatalyst coated with the Cu simple substance.
The polypyrrole nanotube electrocatalyst wrapped by the Cu simple substance prepared by the embodiment has the tube diameter of 190nm and the specific surface area of 820m 2 G, power density of 125mW cm -2 。
Example 8
A preparation method of a polypyrrole nanotube electrocatalyst is characterized by comprising the following steps:
s1: dispersing NiO in water, and stirring until the NiO is completely dissolved to obtain a first solution;
s2: adding 5mmol/L methyl orange into the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second solution;
s3: adding pyrrole monomer into the second solution, wherein the mass ratio of the pyrrole monomer to the ferric chloride is 1; stirring to perform in-situ polymerization reaction to obtain a polypyrrole nanotube wrapped with NiO;
s4: and placing the polypyrrole nanotube wrapped with NiO in a hydrogen atmosphere, and calcining at 600 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Ni simple substance.
The polypyrrole nanotube electrocatalyst coated with the Ni simple substance prepared by the embodiment has the tube diameter of 200nm and the specific surface area of 820m 2 G, power density of 135mW cm -2 。
Example 9
The preparation method of the polypyrrole nanotube electrocatalyst is characterized by comprising the following steps of:
s1: mixing Fe 2 O 3 Dispersing in water, stirring to dissolve completelyPerforming decomposition to obtain a first solution;
s2: adding 5mmol/L methyl orange into the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second solution;
s3: adding pyrrole monomer to the second solution, wherein the mass ratio of the pyrrole monomer to the ferric chloride is 1 2 O 3 The molar ratio of Fe in the alloy is 1; stirring to perform in-situ polymerization reaction to obtain the product coated with Fe 2 O 3 The polypyrrole nanotubes of (a);
s4: wrapping the coating with Fe 2 O 3 The polypyrrole nanotube is placed in a hydrogen atmosphere and calcined at the temperature of 600 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Fe simple substance.
The polypyrrole nanotube electrocatalyst wrapped by the Fe simple substance prepared by the embodiment has the tube diameter of 195nm and the specific surface area of 800m 2 G, power density of 150mW cm -2 。
Example 10
The preparation method of the polypyrrole nanotube electrocatalyst is characterized by comprising the following steps of:
s1: dispersing NiO in water, and stirring until the NiO is completely dissolved to obtain a first solution;
s2: adding 5mmol/L methyl orange into the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second solution;
s3: adding pyrrole monomer into the second solution, wherein the mass ratio of the pyrrole monomer to the ferric chloride is 1; stirring to perform in-situ polymerization reaction to obtain a polypyrrole nanotube wrapped with NiO;
s4: and placing the polypyrrole nanotube wrapped with NiO in a hydrogen atmosphere, and calcining at 600 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Ni simple substance.
The diameter of the polypyrrole nanotube electrocatalyst wrapped with the Ni simple substance prepared by the embodiment is 201nm, and the specific surface area is 810m 2 G, power density of 155mW cm -2 。
Example 11
This example differs from example 10 in that NiCl is added 2 The reaction is carried out.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the polypyrrole nanotube electrocatalyst is characterized by comprising the following steps of:
s1: dispersing an oxide of a transition metal or a soluble salt of the transition metal in water, and stirring until the transition metal is completely dissolved to obtain a first solution;
s2: adding methyl orange into the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second solution;
s3: adding pyrrole monomer into the second solution, stirring and polymerizing to obtain a polypyrrole nanotube wrapped with a transition metal oxide or a transition metal salt;
s4: and calcining the polypyrrole nanotube wrapped with the transition metal oxide or the transition metal salt in a reducing atmosphere to obtain the polypyrrole nanotube electrocatalyst wrapped with the transition metal simple substance.
2. The method of claim 1, wherein the transition metal oxide is CoO, cuO, or Fe 2 O 3 And NiO.
3. The method of claim 1, wherein the soluble salt of the transition metal is CoCl 2 、CuCl 2 、FeCl 3 And NiCl 2 Any one of them.
4. The method for preparing the polypyrrole nanotube electrocatalyst according to claim 1, wherein the pyrrole monomer is purified by reduced pressure distillation before being added into the reaction system; the temperature of the reduced pressure distillation is 80-100 ℃, and the pressure is 0.08MPa.
5. The method of claim 1, wherein the reducing atmosphere comprises a hydrogen atmosphere or a carbon monoxide atmosphere.
6. The method of claim 1, wherein the calcination is carried out at a temperature of 400-600 ℃.
7. The method for preparing the polypyrrole nanotube electrocatalyst according to claim 1, wherein the molar ratio of the pyrrole monomer to the transition metal in the transition metal oxide or soluble salt is 1 (0.5-2.5).
8. The method for preparing the polypyrrole nanotube electrocatalyst according to claim 1, wherein the concentration of methyl orange ranges from 3mmol/L to 5mmol/L, and the ratio of the pyrrole monomer to the ferric chloride is 1 (0.5-2.5).
9. A polypyrrole nanotube electrocatalyst, according to the method of any one of claims 1-8, characterized in that, the specific surface area of the polypyrrole nanotube electrocatalyst is 600-820 m 2 (iv) g; the power density of the polypyrrole nanotube electrocatalyst is 70-154 mW cm -2 。
10. Use of the polypyrrole nanotube electrocatalyst produced by the method of production according to any one of claims 1 to 8 in metal-air batteries.
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| Publication number | Priority date | Publication date | Assignee | Title |
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