CN108963275B - Non-metal self-supporting air electrode and preparation method thereof - Google Patents

Non-metal self-supporting air electrode and preparation method thereof Download PDF

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CN108963275B
CN108963275B CN201810559307.3A CN201810559307A CN108963275B CN 108963275 B CN108963275 B CN 108963275B CN 201810559307 A CN201810559307 A CN 201810559307A CN 108963275 B CN108963275 B CN 108963275B
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carbon
nitrogen
sulfur
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air electrode
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程元徽
郭银建
向中华
张宁远
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Beijing University of Chemical Technology
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
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Abstract

A non-metal self-supporting air electrode and a preparation method thereof belong to the technical field of electrode materials. A carbon material air electrode with oxygen reduction and oxygen precipitation catalytic performance is obtained by using materials containing carbon, nitrogen and sulfur as reactants and then through electropolymerization and high-temperature calcination pyrolysis, has wide application prospect in the fields of metal-air batteries, renewable fuel batteries and the like, and belongs to the technical field of electrode materials.

Description

Non-metal self-supporting air electrode and preparation method thereof
Technical Field
The invention relates to a self-supporting air electrode and a preparation method thereof, in particular to a carbon material air electrode which takes materials containing carbon, nitrogen and sulfur as reactants and is obtained by pre-polymerization and high-temperature calcination pyrolysis and has oxygen reduction and oxygen precipitation catalytic performance, has wide application prospect in the fields of metal-air batteries, renewable fuel batteries and the like, and belongs to the technical field of electrode materials.
Background
The metal-air battery is a new concept fuel battery formed by replacing hydrogen energy with metal fuel, and is expected to become a new generation of green energy. It gives play to the many advantages of fuel cell, providing zinc, aluminium and other metals to the reaction position in the cell like hydrogen, forming a device for continuously producing electric energy with oxygen, having the advantages of no toxicity, no pollution, stable discharge voltage, high specific energy, small internal resistance, long storage life, relatively low price, low technological requirement, high specific power, etc., having abundant cheap resources, regenerative utilization, simple structure compared with hydrogen fuel cell, and being a very good development and application beforeNew energy of scene. The working principle of the method is that metal reacts with oxygen in air to discharge, negative electrode metal loses electrons and is oxidized into metal ions during discharge, and positive electrode oxygen generates reduction reaction under alkaline condition to produce OH-
At present, the anode oxygen electrode catalyst of the metal-air battery mainly comprises noble metals such as Pt, Ru, Au and the like and alloys thereof. Noble metals such as Pt/C, IrO2The catalyst/C and the like has high catalytic performance, but has high price, scarce resources and poor stability, thereby limiting the commercial development and application of the catalyst. Researches show that the functionalized carbon material can catalyze the oxygen reduction reaction, the carbon material nonmetal catalyst prepared by doping nitrogen and sulfur heteroatoms has good catalytic effect, the raw material cost is low, the raw material is easy to obtain, the stability is good, and the heteroatom-doped carbon material catalyst is an important research direction of the oxygen reduction catalyst. However, the low doping amount and the uneven distribution of the doping source restrict further improvement of the performance of the carbon material catalyst. And finally, the self-supporting carbon nano tube air electrode with the performance superior to that of the traditional air electrode is prepared by optimizing the preparation and post-treatment process parameters.
Disclosure of Invention
The technical problem solved by the invention is as follows: the mixing uniformity between the doping source and the carbon source is improved, and the catalytic performance of the carbon-carbon carrier air electrode is further improved. A covalent organic polymer rich in nitrogen and sulfur is synthesized on a carbon carrier by a simple method, the nitrogen and the sulfur are uniformly distributed in the polymer and are tightly combined on the carbon carrier, and carbonization, nitridation and vulcanization are carried out at the high temperature of 800-1000 ℃, so that the nitrogen and sulfur co-doped carbon-based catalytic material which has high-efficiency catalytic performance of oxygen reduction/oxygen precipitation reaction and good stability is obtained. The material has the advantages of simple preparation process, easy operation and low cost, and solves the problems of low catalytic performance, poor stability, high cost and difficult large-scale popularization of the secondary metal air battery catalyst. The invention provides a self-supporting air electrode and a preparation method thereof, which have long cycle life and show high catalytic performance.
The invention is realized by the following modes:
a preparation method of a non-metal self-supporting air electrode is characterized by comprising the following steps:
step 1) directly preparing an organic polymer containing uniformly distributed nitrogen, sulfur and carbon by using a nitrogen source, a sulfur source and a carbon source; weighing a certain amount of nitrogen source, sulfur source and carbon source, mixing and dispersing in a solvent, transferring the mixed solution into an electrolytic tank for reaction, cleaning the generated product for several times by using a cleaning solution after a period of time, and drying to obtain the carbon material and the electrode material containing the nitrogen and sulfur covalent organic polymer;
and 2) transferring the synthesized carbon material and the electrode material containing the nitrogen and sulfur covalent organic polymer into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace for high-temperature calcination for a certain time, carbonizing the porcelain boat in inert gas, and naturally cooling to obtain the nitrogen and sulfur co-doped carbon-based electrode.
Further preferably:
the sulfur-containing compound can be one or more than two of 1,3, 5-benzene trithiophenol, trithiocyanuric acid and 2-amino-5-mercapto-1, 3, 4-thiadiazole in the step 1).
In the step 1), the nitrogen-containing compound can be one or more than two of cyanuric chloride, 2-amino-5-mercapto-1, 3, 4-thiadiazole and melamine. The nitrogen source and the sulfur source may be the same organic matter or may be two organic matters.
And step 1), the carbon-containing compound is one or more than two of carbon paper and carbon cloth.
Step 1), the ratio of the amounts of sulfur in the sulfur source, nitrogen in the nitrogen source, and carbon in the carbon source is preferably 0.1 to 5: 1.5: (50-100), preferably 1: 1.5: (50-80).
Step 1), the reaction polymerization temperature in the electrolytic bath is 20-25 ℃, and 20 ℃ is preferred; the polymerization time is from 1 to 3 hours, preferably 2 hours; the sweeping speed is 50mv/s, and the voltage range is-0.2V-1.7V.
Step 1) in the drying step, vacuum drying is adopted. The vacuum drying temperature is 65-150 deg.C, preferably 60-100 deg.C, and more preferably 60-80 deg.C.
And 2), the inert protective gas used in the calcining pyrolysis process is high-purity nitrogen and argon, and the purity is more than or equal to 99.99%.
Step 2), the temperature of the pyrolysis process is raised to 150-200 ℃ at the speed of 1-10 ℃/min, preferably 200 ℃, and the temperature is maintained for 0.5-2.0 hours, preferably 1 hour, then the temperature is raised to 300-400 ℃ at the speed of 1-10 ℃/min, preferably 350 ℃, and the temperature is maintained for 1-3.0 hours, preferably 2 hours, and finally the temperature is raised to 800-1000 ℃ at the speed of 1-10 ℃/min, preferably 900 ℃, and the temperature is maintained for 1-3.0 hours, preferably 2 hours.
THE ADVANTAGES OF THE PRESENT INVENTION
The invention synthesizes the nitrogen and sulfur double-doped carbon-based non-metal oxygen reduction/precipitation double-effect catalytic material by adopting a simple method, has mild synthesis conditions and simple experimental operation, and the prepared carbon-based electrocatalyst not only has high-efficiency catalytic performance of oxygen reduction and oxygen precipitation reaction, but also has good stability. Provides a new idea for the design of preparing the high-efficiency bifunctional electrocatalytic material of the secondary metal-air battery. Compared with the prior art, the invention has the following advantages.
1) The nitrogen and sulfur co-doped carbon-based electrode is prepared by primary electropolymerization reaction and primary pyrolysis carbonization reaction, the adopted raw materials are cheap and easy to obtain, the reaction condition is mild, the operation is simple and convenient, no pollution is discharged in the process, the environment is friendly, and the large-scale production is easy.
2) The invention takes carbon paper, carbon cloth and other materials as carbon sources, nitrogen and sulfur atoms are uniformly doped in the carbon materials through electropolymerization to generate more active sites, namely, a nitrogen source and a sulfur source react with the carbon cloth of the carbon source to ensure that the nitrogen atoms and the sulfur atoms replace certain carbon atoms on a carbon atom plane, thereby improving the catalytic performance of the carbon materials, simultaneously increasing the conductivity of the carbon materials, promoting the electron transfer and mass transfer, accelerating the processes of oxygen reduction and oxygen precipitation,
3) according to the invention, a nitrogen and sulfur co-doped carbon material is formed through a high-temperature reaction, and the synergistic effect of nitrogen and sulfur promotes the oxygen reduction and oxygen precipitation reaction processes, so that the catalytic performance is better than that of a single heteroatom doped structure.
4) The carbon-based non-metal oxygen reduction/precipitation double-effect catalyst has good double-effect electrocatalysis performance and excellent stability, can simultaneously realize the processes of nitridation, vulcanization, carbonization and the like by only one step, has simple preparation process, and is very suitable for the fields of secondary metal air batteries and the like.
Description of the drawings:
FIG. 1 is a linear scanning voltammogram of an oxygen reduction reaction of a nitrogen-sulfur double-doped self-supporting air electrode double-effect catalyst in an embodiment of the invention.
FIG. 2 is a linear scanning voltammogram of the oxygen evolution reaction of a nitrogen sulfur double-doped self-supporting air electrode double-effect catalyst in an embodiment of the invention.
FIG. 3 is a scanning electron micrograph of a nitrogen sulfur double doped self-supporting air electrode dual-effect catalyst of example 1.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Step 1): cutting a piece of carbon paper of 0.5x0.7cm, washing with deionized water, then immersing into a mixed solution of concentrated sulfuric acid and concentrated nitric acid (40 ml of concentrated sulfuric acid and 20ml of concentrated nitric acid) for 30min, adding 6g of potassium permanganate into the mixed solution, stirring for 1 hour at room temperature, then slowly adding deionized water to 100ml in an ice bath, stirring for 2 hours, finally dropwise adding hydrogen peroxide until the solution becomes clear, taking out the carbon paper, washing with deionized water, and vacuum drying for 12 hours.
Step 2): 0.01g (0.075mmol) of 2-amino-5-mercapto-1, 3, 4-thiadiazole and 0.8ml of concentrated sulfuric acid (96-97 wt%) are weighed and added into 150ml of deionized water, ultrasonic treatment is carried out for 15min until the concentrated sulfuric acid is completely dissolved, then the solution is transferred into an electrolytic cell for electropolymerization, polymerization is carried out for 100 circles, the sweeping speed is 50mv/s, and the voltage range is-0.2V-1.7V. The obtained product was washed with deionized water and then dried in a vacuum oven at 80 ℃ for 12 hours.
Step 3); placing organic polymer material into a porcelain boat, calcining in a high temperature tube furnace with gas flow of 35ml min-1The temperature of the argon is firstly increased to 200 ℃ at the temperature rising speed of 5 ℃/min, the temperature is maintained for 1 hour, then is increased to 350 ℃ at the temperature rising speed of 5 ℃/min, the temperature is maintained for 2 hours, then is increased to 900 ℃ at the temperature rising speed of 5 ℃/min, the temperature is maintained for 2 hours, and finally the temperature is naturally reduced to obtain the nitrogen-sulfur double-doped self-supporting materialAn air electrode.
Example 2
Step 1): cutting a piece of carbon cloth of 0.5x0.7cm, washing with deionized water, immersing into a mixed solution of concentrated sulfuric acid and concentrated nitric acid (40 ml of concentrated sulfuric acid and 20ml of concentrated nitric acid) for 30min, adding 6g of potassium permanganate into the mixed solution, stirring at room temperature for 1 hour, slowly adding deionized water to 100ml in an ice bath, stirring for 2 hours, finally dropwise adding hydrogen peroxide until the solution becomes clear, taking out the carbon cloth, washing with deionized water, and vacuum drying for 12 hours.
Step 2): 0.01g (0.075mmol) of 2-amino-5-mercapto-1, 3, 4-thiadiazole and 0.8ml of concentrated sulfuric acid (96-97 wt%) are weighed and added into 150ml of deionized water, ultrasonic treatment is carried out for 15min until the concentrated sulfuric acid is completely dissolved, then the solution is transferred into an electrolytic cell for electropolymerization, polymerization is carried out for 100 circles, the sweeping speed is 50mv/s, and the voltage range is-0.2V-1.7V. The obtained product was washed with deionized water and then dried in a vacuum oven at 80 ℃ for 12 hours.
Step 3); placing organic polymer material into a porcelain boat, calcining in a high temperature tube furnace with gas flow of 35ml min-1And (3) heating the argon to 200 ℃ at the heating rate of 5 ℃/min, preserving heat for 1 hour, heating the argon to 350 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, heating the argon to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain the nitrogen-sulfur double-doped self-supporting air electrode.
Example 3
Step 1): cutting a piece of carbon paper of 0.5x0.7cm, washing with deionized water, then immersing into a mixed solution of concentrated sulfuric acid and concentrated nitric acid (40 ml of concentrated sulfuric acid and 20ml of concentrated nitric acid) for 30min, adding 6g of potassium permanganate into the mixed solution, stirring for 1 hour at room temperature, then slowly adding deionized water to 100ml in an ice bath, stirring for 2 hours, finally dropwise adding hydrogen peroxide until the solution becomes clear, taking out the carbon paper, washing with deionized water, and vacuum drying for 12 hours.
Step 2): 0.005g (0.0375mmol) of 2-amino-5-mercapto-1, 3, 4-thiadiazole and 0.8ml of concentrated sulfuric acid (96-97 wt%) are weighed and added into 150ml of deionized water, ultrasonic treatment is carried out for 15min until the concentrated sulfuric acid is completely dissolved, then the solution is transferred into an electrolytic cell for electropolymerization, polymerization is carried out for 100 circles, the sweeping speed is 50mv/s, and the voltage range is-0.2V-1.7V. The obtained product was washed with deionized water and then dried in a vacuum oven at 80 ℃ for 12 hours.
Step 3); placing organic polymer material into a porcelain boat, calcining in a high temperature tube furnace with gas flow of 35ml min-1And (3) heating the argon to 200 ℃ at the heating rate of 5 ℃/min, preserving heat for 1 hour, heating the argon to 350 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, heating the argon to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain the nitrogen-sulfur double-doped self-supporting air electrode.
Example 4
Step 1): cutting a piece of carbon cloth of 0.5x0.7cm, washing with deionized water, immersing into a mixed solution of concentrated sulfuric acid and concentrated nitric acid (40 ml of concentrated sulfuric acid and 20ml of concentrated nitric acid) for 30min, adding 6g of potassium permanganate into the mixed solution, stirring at room temperature for 1 hour, slowly adding deionized water to 100ml in an ice bath, stirring for 2 hours, finally dropwise adding hydrogen peroxide until the solution becomes clear, taking out the carbon cloth, washing with deionized water, and vacuum drying for 12 hours.
Step 2): 0.005g (0.0375mmol) of 2-amino-5-mercapto-1, 3, 4-thiadiazole and 0.8ml of concentrated sulfuric acid (96-97 wt%) are weighed and added into 150ml of deionized water, ultrasonic treatment is carried out for 15min until the concentrated sulfuric acid is completely dissolved, then the solution is transferred into an electrolytic cell for electropolymerization, polymerization is carried out for 100 circles, the sweeping speed is 50mv/s, and the voltage range is-0.2V-1.7V. The obtained product was washed with deionized water and then dried in a vacuum oven at 80 ℃ for 12 hours.
Step 3); placing organic polymer material into a porcelain boat, calcining in a high temperature tube furnace with gas flow of 35ml min-1And (3) heating the argon to 200 ℃ at the heating rate of 5 ℃/min, preserving heat for 1 hour, heating the argon to 350 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, heating the argon to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain the nitrogen-sulfur double-doped self-supporting air electrode.

Claims (8)

1. A preparation method of a nonmetal self-supporting air electrode with catalytic performance of oxygen reduction/oxygen precipitation reaction is characterized by comprising the following steps:
step 1) directly preparing an organic polymer containing uniformly distributed nitrogen, sulfur and carbon by using a nitrogen source, a sulfur source and a carbon source; weighing a certain amount of nitrogen source, sulfur source and carbon source, mixing and dispersing in a solvent, transferring the mixed solution into an electrolytic tank for polymerization reaction, cleaning the generated product for several times by using a cleaning solution after a period of time, and drying to obtain the carbon material and the electrode material containing the nitrogen and sulfur covalent organic polymer;
step 2) transferring the synthesized carbon material and the electrode material containing the nitrogen and sulfur covalent organic polymer into a porcelain boat, placing the porcelain boat into a high-temperature tube furnace for high-temperature calcination for a certain time, carbonizing the porcelain boat in inert gas, and naturally cooling to obtain the nitrogen and sulfur co-doped carbon-based electrode;
step 1), the sulfur source is one or more than two of 1,3, 5-benzene trithiophenol, trithiocyanuric acid and 2-amino-5-mercapto-1, 3, 4-thiadiazole;
the nitrogen source in the step 1) is one or more than two of trichlorocyanamide, 2-amino-5-mercapto-1, 3, 4-thiadiazole and melamine;
step 1), the carbon source is one or two of carbon paper and carbon cloth;
step 1), the reaction polymerization temperature in the electrolytic bath is 20-25 ℃; the polymerization time is 1-3 hours; the sweeping speed is 50mv/s, and the voltage range is-0.2V-1.7V.
2. The method for preparing a non-metallic self-supporting air electrode having catalytic performance for oxygen reduction/oxygen evolution reaction as claimed in claim 1, wherein the nitrogen source and the sulfur source are the same organic substance or two organic substances.
3. The method for preparing a non-metallic self-supporting air electrode having catalytic performance of oxygen reduction/oxygen evolution reaction according to claim 1, wherein in step 1), the ratio of the amounts of sulfur in the sulfur source, nitrogen in the nitrogen source and carbon in the carbon source is 0.1 to 5: 1.5: (50-100).
4. The method for preparing a non-metallic self-supporting air electrode having catalytic performance of oxygen reduction/oxygen evolution reaction according to claim 1, wherein the ratio of the amounts of the sulfur element in the sulfur source, the nitrogen element in the nitrogen source and the carbon element in the carbon source is 1: 1.5: (50-80).
5. The method for preparing a non-metal self-supporting air electrode having catalytic performance of oxygen reduction/oxygen evolution reaction according to claim 1, wherein the step 1) is a drying step in which vacuum drying is performed at a temperature of 65-150 ℃.
6. The method for preparing the non-metal self-supporting air electrode with the catalytic performance of the oxygen reduction/oxygen evolution reaction according to claim 1, wherein in the step 2), the inert protective gas used in the calcining process is high-purity nitrogen and argon, and the purity is more than or equal to 99.99 percent; step 2), the temperature is raised to 150-.
7. The method for preparing a non-metal self-supporting air electrode with catalytic performance of oxygen reduction/oxygen evolution reaction according to claim 6, wherein the calcination process comprises heating to 200 ℃ at a rate of 1-10 ℃/min, maintaining the temperature for 1 hour, heating to 350 ℃ at a rate of 1-10 ℃/min, maintaining the temperature for 2 hours, and finally heating to 900 ℃ at a rate of 1-10 ℃/min, and maintaining the temperature for 2 hours.
8. A non-metallic self-supporting air electrode prepared according to the method of any one of claims 1 to 7.
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