CN115207378B - 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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Abstract
The application 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 or the soluble salt of 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 polypyrrole nanotube coated with transition metal oxide or transition metal salt; 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 good electronic conductivity and mechanical strength of the gas channel.
Description
Technical Field
The application belongs to the field of battery electrode materials, and relates to a polypyrrole nanotube electrocatalyst, a preparation method and application thereof.
Background
Batteries are a green sustainable energy technology that is conforming to the demands of today's society. Among them, the metal-air battery has the advantages of high theoretical energy density, good safety, low cost, green environmental protection, and the like, and is paid attention to. The choice of the electrocatalyst electrode material for a metal-air battery is critical to the 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. The current commonly used electrocatalyst is a noble metal catalyst represented by Pt, ir and the like, but noble metal resources are rare, the cost is high, and industrial application is difficult. The transition metal compound has the advantages of rich crust reserves, low price, strong alkali resistance, strong oxidation resistance and the like, and becomes a research hot spot as an efficient non-noble metal catalyst. However, such catalysts currently have the disadvantages of poor conductivity, low exposure rate of the catalytic active sites, and the like, resulting in unsatisfactory catalytic performance.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a polypyrrole nanotube electrocatalyst, a preparation method and application thereof, wherein polypyrrole serving as a conductive polymer has good conductivity so as to be beneficial to electron transmission, a tubular structure provides a high specific surface area, and catalytic active sites are increased. Thus, the electrocatalyst which has good catalytic performance, high specific surface area and porosity and good electronic conductivity and mechanical strength of the gas channel is obtained.
The application is realized by the following technical scheme:
the preparation process of polypyrrole nanotube electrocatalyst includes 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 or the soluble salt of 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 polypyrrole nanotube coated with transition metal oxide or transition metal salt;
s4: 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.
Preferably, the oxide of the transition metal is CoO, cuO, fe 2 O 3 And any one of NiO.
Preferably, the soluble salt of the transition metal is CoCl 2 、CuCl 2 、FeCl 3 And NiCl 2 Any one of the following.
Preferably, the pyrrole monomer is purified by adopting a reduced pressure distillation mode before being added into a reaction system; the temperature of reduced pressure distillation is 80-100 ℃ and the pressure is 0.08MPa.
Preferably, the reducing atmosphere includes a hydrogen atmosphere or a carbon monoxide atmosphere.
Preferably, the calcination temperature is 400-600 ℃.
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 to 2.5).
Preferably, the concentration of the methyl orange is in the range of 3mmol/L to 5mmol/L, and the ratio of the pyrrole monomer to the ferric chloride substance is 1 (0.5 to 2.5).
The polypyrrole nanotube electrocatalyst prepared by the method has a specific surface area of 600-820 m 2 /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 metal-air batteries.
Compared with the prior art, the application has the following beneficial technical effects:
the preparation method of polypyrrole nanotube electrocatalyst adopts methyl orange as soft template agent, ferric chloride as oxidant, and pyrrole monomer is polymerized to prepare polypyrrole nanotube, and the tubular structure can be used as gas channel to raise the catalytic efficiency of metal-air cell electrocatalyst, and at the same time, transition metal oxide or transition metal soluble salt is added into the reaction system, and in the course of synthesizing polypyrrole nanotube, the transition metal oxide or transition metal soluble salt is in-situ coated in the interior of polypyrrole nanotube, and at the same time, the polypyrrole nanotube coated with transition metal simple substance is obtained by calcining in reducing atmosphere, and in the course of calcining the polypyrrole nanotube the more stable nitrogen-carbon (N-C) structure is formed, so that the (metal-nitrogen-carbon) M-N-C 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 good electronic conductivity and mechanical strength of the gas channel.
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.
Further, the calcination temperature is 400-600 ℃, so that 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 into a transition metal simple substance in a reducing atmosphere.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing polypyrrole nanotube electrocatalyst according to the application;
fig. 2 is an SEM image of polypyrrole nanotube electrocatalyst prepared in example 3 of the present application at different magnifications.
FIG. 3 is a TEM image of polypyrrole nanotube electrocatalyst made in example 3 of the present application.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present application, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, 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 application belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the application in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, "comprising," "including," "having," or similar terms encompass the meanings of "consisting of … …" and "consisting essentially of … …," e.g., "a includes a" encompasses the meanings of "a includes a and the other and" a includes a only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
Studies have shown that the direct use of non-noble metals as electrocatalysts is inefficient in catalysis, and that catalytic efficiency is currently improved mainly by doping, mainly comprising transition metal heteroatom co-doped carbon, and heteroatom doping of N, B, S, O, P, etc. Currently, in nonmetallic doping modification, nitrogen atoms may be doped to the edges or inside of the carbon structure, due to the similarity in size of nitrogen and carbon atoms, creating corresponding active sites. Because nitrogen doping is easier to realize than other hetero-atom doping processes and a plurality of corresponding active sites can be generated, the transition metal and nitrogen doped carbon catalyst becomes a catalyst which has higher practical value and is more hopeful to replace noble metal, and is called as a transition metal and nitrogen modified carbon catalyst, namely an M-N-C catalyst for short. Such heteroatom-modified carbon catalytic materials are considered as potential alternatives to noble metal catalysts due to their low cost, stability and good electrical conductivity. However, the M-N-C catalysts reported in the current research have the defects of complex synthetic route and non-ideal catalytic efficiency.
According to the application, polypyrrole is selected as a base material, and the polypyrrole has an N-C structure molecular base, so that the electronic conductivity of the catalyst can be effectively improved, and high catalytic efficiency can be achieved. Meanwhile, the polymerization process of polypyrrole can realize various shapes such as round tube shape, square tube shape and the like through the induction of the template agent, and the natural pore canal structures can be used as gas channels, so that the catalytic efficiency of the metal-air battery electrocatalyst is improved. And the pore size of the polypyrrole nanotube can be adjusted by controlling the reaction conditions, so that the shape and the pipe diameter of the polypyrrole nanotube can be adjusted and controlled according to the practical application conditions by taking the polypyrrole nanotube as a loading agent of transition metal, thereby adjusting and controlling the loading amount and the gas flux of the catalyst. The polypyrrole is used as a conductive polymer, has the advantages of high electronic conductivity and high mechanical strength, and can prepare the polypyrrole nanotube with a hollow structure by controlling reaction conditions so as to achieve high specific surface area. Meanwhile, polypyrrole has anti-corrosion performance. 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 or the soluble salt of the transition metal is completely dissolved to obtain a first solution;
wherein the oxide of the transition metal comprises CoO, cuO, fe 2 O 3 And any one of NiO. Soluble salts of transition metals include CoCl 2 、CuCl 2 、FeCl 3 And NiCl 2 Any one of the following. The mole 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 polypyrrole nanotube coated with transition metal oxide or transition metal salt; wherein the 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 reduced pressure distillation is 80-100 ℃ and the pressure is 0.08MPa.
S4: 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.
Wherein the reducing atmosphere comprises a hydrogen atmosphere or a carbon monoxide atmosphere; the calcination temperature is 400-600 ℃.
The pipe diameter of the polypyrrole nanotube electrocatalyst prepared by the method is 80-200nm, and the specific surface area is 600-820 m 2 /g; the power density is 70-154 mW.cm -2 。
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present application and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
Example 1
Purifying pyrrole monomer by vacuum distillation method, and reducing pressureThe distillation temperature was 80℃and the pressure was 0.08MPa. 0.55g CuCl was taken 2 Dispersing in 300mL deionized water, stirring at normal temperature for 30min to dissolve completely. 300mg of methyl orange is taken and dissolved in 300mL of the solution, and the solution is stirred for 5 hours at normal temperature until the solution turns into clear pink, then 2.22g of ferric trichloride hexahydrate is slowly added, and the solution immediately shows dark red flocculent precipitate. Continuously and rapidly stirring for 50min, adding 1.1g of pyrrole monomer, observing the solution to turn black and green, and polymerizing at room temperature (25 ℃) for 24h by an in-situ polymerization method to obtain the CuCl coated with the CuCl 2 Polypyrrole nanotubes of (a). Filtering, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, and removing the template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, until the pH value is neutral, and drying. Coating CuCl after drying 2 The polypyrrole nanotube is placed in hydrogen atmosphere and calcined at 400 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with Cu simple substance.
The polypyrrole nanotube electrocatalyst coated with Cu simple substance prepared in the embodiment has a pipe diameter of 80nm and a specific surface area of 600m 2 Per gram, a 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 CuCl was taken 2 Dispersing in 490mL deionized water, stirring at normal temperature for 30min to dissolve completely. 300mg of methyl orange is taken and dissolved in 300mL of the solution, and the solution is stirred for 5 hours at normal temperature until the solution turns into clear pink, then 2.22g of ferric trichloride hexahydrate is slowly added, and the solution immediately shows dark red flocculent precipitate. Continuously and rapidly stirring for 50min, adding 1.1g of pyrrole monomer, observing the solution to turn black and green, and polymerizing at room temperature (25 ℃) for 24h by an in-situ polymerization method to obtain the CuCl coated with the CuCl 2 Polypyrrole nanotubes of (a). Filtering, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, and removing the template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, until the pH value is neutral, and drying. Coating CuCl after drying 2 The polypyrrole nanotube is placed in hydrogen atmosphere and calcined at 440 ℃ to obtainPolypyrrole nanotube electrocatalyst coated with Cu simple substance.
The polypyrrole nanotube electrocatalyst coated with Cu simple substance prepared in the embodiment has a pipe diameter of 100nm and a specific surface area of 700m 2 Per gram, a 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 CuCl was taken 2 Dispersing in 490mL deionized water, stirring at normal temperature for 30min to dissolve completely. 300mg of methyl orange is taken and dissolved in 300mL of the solution, and the solution is stirred for 5 hours at normal temperature until the solution turns into clear pink, then 6.65g of ferric trichloride hexahydrate is slowly added, and the solution immediately shows dark red flocculent precipitate. Continuously and rapidly stirring for 50min, adding 1.1g of pyrrole monomer, observing the solution to turn black and green, and polymerizing at room temperature (25 ℃) for 24h by an in-situ polymerization method to obtain the CuCl coated with the CuCl 2 Polypyrrole nanotubes of (a). Filtering, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, and removing the template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, until the pH value is neutral, and drying. Coating CuCl after drying 2 The polypyrrole nanotube is placed in a hydrogen atmosphere and calcined at 550 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with Cu simple substance.
The polypyrrole nanotube electrocatalyst coated with Cu simple substance prepared in the embodiment has the pipe diameter of 120nm and the specific surface area of 720m 2 Per gram, a power density of 80 mW.cm -2 。
The SEM image of the polypyrrole nanotube coated with the Cu simple substance is shown in fig. 2, the TEM image is shown in fig. 3, and 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 reduced pressure distillation temperature is 95 ℃ and the pressure is 0.08MPa. 1.65g CoCl was taken 2 Dispersing in 490mL deionized water, stirring at normal temperature for 30min to dissolve completely. 300mg of methyl orange is dissolved in 300mL to the above solution, stirring at room temperature for 5 hours until the solution turned to a clear pink color, then slowly adding 6.65g of ferric trichloride hexahydrate, and immediately appearing a dark red flocculent precipitate. Continuously stirring for 50min, adding 1.1g pyrrole monomer, observing the solution to turn black and green, and polymerizing at room temperature (25deg.C) for 24 hr by in situ polymerization to obtain CoCl-coated polymer 2 Polypyrrole nanotubes of (a). Filtering, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, and removing the template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, until the pH value is neutral, and drying. Coating the obtained product after drying with CoCl 2 The polypyrrole nanotube is placed in hydrogen atmosphere and calcined at 450 ℃ to obtain the polypyrrole nanotube electrocatalyst coated with Co metal simple substance.
The polypyrrole nanotube electrocatalyst coated with Co simple substance prepared in the embodiment has the pipe diameter of 140nm and the specific surface area of 750m 2 Per gram, a power density of 90mW cm -2 。
Example 5
The pyrrole monomer is purified by a reduced pressure distillation method, wherein the reduced pressure distillation temperature is 85 ℃ and the pressure is 0.08MPa. 1.65g CoO was dispersed in 490mL deionized water and stirred at room temperature for 30min to dissolve completely. 300mg of methyl orange is taken and dissolved in 300mL of the solution, and the solution is stirred for 5 hours at normal temperature until the solution turns into clear pink, then 6.65g of ferric trichloride hexahydrate is slowly added, and the solution immediately shows dark red flocculent precipitate. And continuously and rapidly stirring for 50min, adding 1.1g of pyrrole monomer, observing the solution to turn black and green, and polymerizing for 24h at room temperature (25 ℃) by an in-situ polymerization method to obtain the polypyrrole nanotube wrapped with CoO. Filtering, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, and removing the template, unreacted pyrrole monomer and FeCl 3 ·6H 2 And O, until the pH value is neutral, and drying. And placing the polypyrrole nanotube coated with the CoO obtained after drying in a hydrogen atmosphere, and calcining at 470 ℃ to obtain the polypyrrole nanotube electrocatalyst coated with the Co simple substance.
The polypyrrole nanotube electrocatalyst coated with Co simple substance prepared in the embodiment has the pipe diameter of 160nm and the specific surface area of 780m 2 Per gram, a 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 the ferric chloride is 1:0.5, and the molar ratio of the pyrrole monomer to Co is 1:0.5; stirring to perform in-situ polymerization reaction to obtain polypyrrole nanotubes wrapped with CoO;
s4: and placing the polypyrrole nanotube wrapped with the CoO in a carbon monoxide atmosphere, and calcining at 400 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Co simple substance.
The polypyrrole nanotube electrocatalyst coated with Co simple substance prepared in the embodiment has the pipe diameter of 180nm and the specific surface area of 800m 2 Per gram, a power density of 115mW cm -2 。
Example 7
The preparation method of the polypyrrole nanotube electrocatalyst is characterized by comprising the following steps of:
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 1:1.5, and the molar ratio of the pyrrole monomer to Cu is 1:1; stirring to perform in-situ polymerization reaction to obtain a polypyrrole nanotube wrapped with CuO;
s4: and placing the polypyrrole nanotube wrapped with the CuO in a carbon monoxide atmosphere, and calcining at 500 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with the Cu simple substance.
The polypyrrole nanotube electrocatalyst coated with Cu simple substance prepared in the embodiment has the pipe diameter of 190nm and the specific surface area of 820m 2 Per gram, a power density of 125mW cm -2 。
Example 8
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 1:2, and the molar ratio of the pyrrole monomer to Ni is 1:1.5; 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 Ni simple substance.
The polypyrrole nanotube electrocatalyst coated with Ni simple substance prepared in the embodiment has a pipe diameter of 200nm and a specific surface area of 820m 2 Per gram, a 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: fe is added to 2 O 3 Dispersing in water, stirring to dissolve completely 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 and ferric chloride into the second solution, wherein the ratio of the pyrrole monomer to the ferric chloride is 1:2, and the pyrrole monomer to the Fe 2 O 3 The molar ratio of Fe in the alloy is 1:2.5; stirring to perform in-situ polymerization reaction to obtain the Fe-coated alloy 2 O 3 Polypyrrole nanotubes of (a);
s4: wrapping the Fe with 2 O 3 The polypyrrole nanotube is placed in hydrogen atmosphere and calcined at 600 ℃ to obtain the polypyrrole nanotube electrocatalyst wrapped with Fe simple substance.
The polypyrrole nanotube electrocatalyst coated with Fe simple substance prepared in the embodiment has a pipe diameter of 195nm and a specific surface area of 800m 2 Per gram, a 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 ratio of the pyrrole monomer to the ferric chloride is 1:2.5, and the molar ratio of the pyrrole monomer to Ni in NiO is 1:2.5; 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 Ni simple substance.
The polypyrrole nanotube electrocatalyst coated with Ni simple substance prepared in the embodiment has the pipe diameter of 201nm and the specific surface area of 810m 2 Per gram, a power density of 155mW cm -2 。
Example 11
The difference between this example and example 10 is the addition of NiCl 2 The reaction is carried out.
The foregoing is merely a preferred embodiment of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application, which are intended to be comprehended within the scope of the present application.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present application.
Claims (7)
1. The preparation method of the polypyrrole nanotube electrocatalyst coated with the transition metal simple substance is characterized by comprising the following steps of:
s1: dispersing an oxide of a transition metal in water, stirring to obtain a first dispersion liquid, or dispersing a soluble salt of the transition metal in water, and stirring until the soluble salt is completely dissolved to obtain a first solution;
s2: adding methyl orange into the first dispersion liquid or the first solution, stirring until the methyl orange is completely dissolved, and adding ferric chloride to obtain a second dispersion liquid or a second solution;
s3: adding pyrrole monomer into the second dispersion liquid or the second solution, stirring and polymerizing to obtain polypyrrole nanotube coated with transition metal oxide or transition metal salt;
s4: calcining the polypyrrole nanotube wrapped with the transition metal oxide or the transition metal salt in a reducing atmosphere to obtain a polypyrrole nanotube electrocatalyst wrapped with a transition metal simple substance;
the calcining temperature is 400-600 ℃;
the mole 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);
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 substance is 1 (0.5-2.5);
the pipe diameter of the polypyrrole nanotube electrocatalyst is 80-200 nm;
the transition metal is Co, cu, fe or Ni.
2. Polypyrrole nanotube electrocatalyst coated with elemental transition metal according to claim 1Characterized in that the oxide of the transition metal is CoO, cuO, fe 2 O 3 And any one of NiO.
3. The method for preparing polypyrrole nanotube electrocatalyst coated with transition metal element according to claim 1, wherein the soluble salt of transition metal is CoCl 2 、CuCl 2 、FeCl 3 And NiCl 2 Any one of the following.
4. The method for preparing the polypyrrole nanotube electrocatalyst coated with the transition metal simple substance according to claim 1, wherein the pyrrole monomer is purified by vacuum distillation before being added into a reaction system; the temperature of reduced pressure distillation is 80-100 ℃ and the pressure is 0.08MPa.
5. The method for preparing the polypyrrole nanotube electrocatalyst coated with the transition metal element according to claim 1, wherein the reducing atmosphere comprises a hydrogen atmosphere or a carbon monoxide atmosphere.
6. The polypyrrole nanotube electrocatalyst coated with transition metal element prepared by the method of any one of claims 1 to 5, wherein the polypyrrole nanotube electrocatalyst has a specific surface area of 600 to 820 2 /g; the power density of the polypyrrole nanotube electrocatalyst is 70-154 mW.cm -2 。
7. The polypyrrole nanotube electrocatalyst coated with transition metal element prepared by the preparation method of any one of claims 1 to 5, and application thereof in metal-air batteries.
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