CN108963275A - A kind of nonmetallic self-supporting air electrode and preparation method thereof - Google Patents
A kind of nonmetallic self-supporting air electrode and preparation method thereof Download PDFInfo
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- H01M4/00—Electrodes
- 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
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- H01M4/90—Selection of catalytic material
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Abstract
A kind of nonmetallic self-supporting air electrode and preparation method thereof, belongs to electrode material technical field.It is a kind of using carbon containing, nitrogen, sulphur material as reactant, then the method being pyrolyzed through electropolymerization and high-temperature calcination obtains, and there is hydrogen reduction and its oxygen the carbon material air electrode of catalytic performance is precipitated, it has broad application prospects in fields such as metal-air battery, regeneratable fuel cells, belongs to electrode material technical field.
Description
Technical field
Invention is related to a kind of self-supporting air electrode and preparation method thereof, and in particular to a kind of to utilize carbon containing, nitrogen, the material of sulphur
Material is used as reactant, and the method being then pyrolyzed through pre-polymerization and high-temperature calcination obtains, and there is hydrogen reduction and its oxygen catalytic performance is precipitated
Carbon material air electrode, have broad application prospects, belong in fields such as metal-air battery, regeneratable fuel cells
Electrode material technical field.
Background technique
Metal-air battery is a kind of fuel cell for the new concept for replacing hydrogen energy source with metal fuel and being formed, and is expected to
As the new generation of green energy.Its many merits for having played fuel cell provides the metals such as zinc, aluminium to electricity as hydrogen
Response location in pond constitutes the device of a continuous production electric energy with oxygen, there is nontoxic and pollution-free, discharging voltage balance,
The advantages that high-energy-density, internal resistance is small, and storage life is long, and price is relatively low, and process specifications are lower, high-specific-power, it is existing
Low-cost resource abundant, and energy regeneration, it is simpler than hydrogen fuel cell structure, it is the new energy for having very much development and application prospect
Source.Its working principle is to be reacted and discharged with the oxygen in air using metal, and negative metal loses electronics when electric discharge
Oxidation becomes metal ion, and reduction reaction production OH occurs under alkaline condition for positive oxygen-
Metal-air battery anode oxygen electrode catalyst is based on the noble metals such as Pt, Ru, Au and its alloy at present.Your gold
Belong to such as Pt/C, IrO2Although the catalytic performances such as/C are high, expensive, scarcity of resources, stability are poor, to limit its quotient
Industryization development and application.Research shows that the progress that the carbon material after functionalization can be reacted with catalytic oxidation-reduction, by adulterating nitrogen, sulphur
The carbon material non-metallic catalyst that hetero atom is prepared not only has good catalytic effect, but also cost of material is low and is easy to get,
Stability is good, and therefore, it has become the important research directions of oxygen reduction catalyst for the carbon material catalyst of Heteroatom doping.However, mixing
Miscellaneous amount is low, and doped source uneven distribution constrains further increasing for carbon material catalyst performance.Finally, by optimization preparation and
Aftertreatment technology parameter is prepared for the freestanding carbon nanotube air electrode that performance is better than conventional air electrode.
Summary of the invention
Technical problem solved by the invention is: improving the mixing uniformity between doped source and carbon source, further increases
The catalytic performance of carbon carbon carrier air electrode.Synthesize on the carbon carrier by simple method it is a kind of rich in nitrogen, sulphur covalently have
Machine polymer, nitrogen, sulphur are evenly distributed in the polymer and combine closely on the carbon carrier, carries out at 800-1000 DEG C of high temperature
Carbonization, nitridation, vulcanization, are not only possessed efficient hydrogen reduction/oxygen evolution reaction catalytic performance, while being had good steady
Qualitative nitrogen, the carbon-based catalysis material of sulphur codope.The material preparation process is simple, easy to operate, low in cost, solves secondary gold
Category air cell catalyst catalytic performance is not high, and stability is poor, the problem of being difficult to large-scale promotion at high cost.The present invention provides
A kind of self-supporting air electrode and preparation method thereof, has extended cycle life, presents very high catalytic performance.
The present invention is achieved in the following ways:
A kind of preparation method of nonmetallic self-supporting air electrode, which comprises the following steps:
Step 1) is directly prepared using nitrogen source, sulphur source, carbon source containing nitrogen, sulphur, the equally distributed organic polymer of carbon；It weighs
A certain amount of nitrogen source, sulphur source, carbon source are mixed and are scattered in solvent, then the mixed liquor is transferred in electrolytic cell and is reacted,
After a period of time, generates product and cleaned for several times with cleaning solution, it is dry to obtain carbon material and nitrogenous, the covalent organic polymer of sulphur electricity
Pole material；
The carbon material of synthesis and nitrogenous, the covalent organic polymer of sulphur electrode material are transferred in porcelain boat by step 2), and
It is put into high temperature process furnances high temperature calcining certain time, it is made to be carbonized in inert gas, natural cooling obtains nitrogen sulphur and is co-doped with
Miscellaneous carbon-based electrode.
It is further preferred:
Step 1), the sulfur-containing compound can be 1,3,5- benzene, three thiophenol, trithiocyanuric acid, sulfydryl -1 2- amino -5-,
One or more of 3,4- thiadiazoles.
Step 1), described in nitrogenous compound can be triphosphazene, 2- amino -5- sulfydryl -1,3,4- thiadiazoles, trimerization
The one or more of cyanamide.Nitrogen source and sulphur source can be same organic matter, be also possible to two kinds of organic matters.
Step 1), the carbon compound are the one or more of carbon paper, carbon cloth.
Step 1), element sulphur in sulphur source, the ratio between amount of substance of carbon is preferably in nitrogen and carbon source in nitrogen source
0.1-5:1.5:(50-100), preferably 1:1.5:(50-80).
Step 1), reactive polymeric temperature is 20-25 DEG C, preferably 20 DEG C in electrolytic cell；Polymerization time be 1-3 hours, preferably 2
Hour；Sweeping speed is 50mv/s, voltage range -0.2V -1.7V.
Step 1) is in drying steps, using vacuum drying.Vacuum drying temperature be 65-150 DEG C, preferably 60-100 DEG C,
More preferably 60-80 DEG C.
Step 2), inert protective gas used in the fumed pyrogenic process are high pure nitrogen, argon gas, purity >=
99.99%.
Step 2), the pyrolytic process are warming up to 150-200 DEG C, preferably 200 DEG C with the rate of 1-10 DEG C/min, heat preservation
0.5-2.0 hours, preferably 1 hour, then 300-400 DEG C, preferably 350 DEG C are warming up to the rate of 1-10 DEG C/min, keep the temperature 1-3.0
Hour, preferably 2 hours, 800-1000 DEG C, preferably 900 DEG C are finally warming up to the rate of 1-10 DEG C/min again, heat preservation 1-3.0 is small
When, preferably 2 hours.
Advantages of the present invention
The present invention has synthesized carbon-based nonmetallic hydrogen reduction/precipitation economic benefits and social benefits catalysis of nitrogen, sulphur codope using easy method
Material, synthesis condition is mild, and experimental implementation is simple, and the carbon-based elctro-catalyst of preparation not only possesses efficient hydrogen reduction and oxygen is precipitated
Reacting catalytic performance, meanwhile, it is with good stability.To prepare the efficiently difunctional electrocatalysis material of secondary metals air cell
Design provide new thinking.Compared with the prior art, the present invention has the advantages that.
1) present invention prepares nitrogen, the carbon-based electricity of sulphur codope by an electric polymerization reaction and primary pyrolysis carburizing reagent
Pole, cheap and easy to get using raw material, reaction condition is mild, easy to operate, and non-pollution discharge in the process, environmentally friendly, is easy to
Amplification production.
2) present invention is using materials such as carbon paper, carbon cloths as carbon source, by electropolymerization by nitrogen sulphur atom Uniform Doped in carbon material
In produce more active sites, i.e., nitrogen source sulphur source is reacted with the carbon cloth carbon paper of carbon source makes nitrogen-atoms and sulphur atom replace carbon atom
Certain carbon atoms of plane, improve its catalytic performance, and carbon material increases electric conductivity at the same time, promote electronics transfer and quality
Transmitting, accelerates hydrogen reduction and oxygen precipitation process,
3) synergistic effect of the carbon material of the invention that nitrogen, sulphur codope are formd by pyroreaction, nitrogen and sulphur promotes
Hydrogen reduction and oxygen evolution reaction process, the catalytic performance than single Heteroatom doping structure are good.
4) present invention has good economic benefits and social benefits electro-catalysis as a kind of carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst
Performance and superior stability only need a step that nitridation, the processes such as vulcanization and carbonization can be achieved at the same time, and preparation process is simple, non-
Often suitable for fields such as secondary metals air cells.
Detailed description of the invention:
Fig. 1 is that a kind of hydrogen reduction of the self-supporting air electrode dual purpose catalyst of nitrogen sulphur codope is anti-in the embodiment of the present invention
The linear sweep voltammetry figure answered.
Fig. 2 is that a kind of oxygen precipitation of the self-supporting air electrode dual purpose catalyst of nitrogen sulphur codope is anti-in the embodiment of the present invention
The linear sweep voltammetry figure answered.
Fig. 3 is a kind of scanning electron microscope (SEM) photograph of the self-supporting air electrode dual purpose catalyst of the nitrogen sulphur codope of embodiment 1.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
Step 1): cutting the carbon paper of one piece of 0.5x0.7cm, after being cleaned with deionized water, is then immersed in the concentrated sulfuric acid and dense nitre
(concentrated sulfuric acid 40ml, concentrated nitric acid 20ml) 30min in the mixed liquor of acid, then 6g potassium permanganate is added in mixed liquor and is stirred at room temperature
It mixes 1 hour, deionized water is then slowly added under ice bath to 100ml, and stir 2 hours, hydrogen peroxide is finally added dropwise to molten
Liquid becomes clear, takes out carbon paper and is washed with deionized water, and is dried in vacuo 12 hours.
Step 2): 0.01g (0.075mmol) 2- amino -5- sulfydryl -1,3,4- thiadiazoles, the 0.8ml concentrated sulfuric acid (96- are weighed
It 97wt%) is added in 150ml deionized water, ultrasonic 15min to whole dissolutions is then transferred into electrolytic cell and carries out voltolisation
It closes, 100 circle of polymerization, sweeping speed is 50mv/s, voltage range -0.2V -1.7V.Obtained product is placed after being washed with deionized water
It is 12 hours dry in 80 DEG C of vacuum ovens.
Step 3)；Organic polymer material is put into porcelain boat in high temperature process furnances to calcine, gas flow is 35ml min-1
Argon gas, be first warming up to 200 DEG C with 5 DEG C/min heating rate, keep the temperature 1 hour, then be warming up to 350 DEG C with 5 DEG C/min, heat preservation 2
Hour, be then warming up to 900 DEG C with 5 DEG C/min heating rate, keep the temperature 2 hours, last Temperature fall nitrogen sulphur codope
Self-supporting air electrode.
Embodiment 2
Step 1): cutting the carbon cloth of one piece of 0.5x0.7cm, after being cleaned with deionized water, is then immersed in the concentrated sulfuric acid and dense nitre
(concentrated sulfuric acid 40ml, concentrated nitric acid 20ml) 30min in the mixed liquor of acid, then 6g potassium permanganate is added in mixed liquor and is stirred at room temperature
It mixes 1 hour, deionized water is then slowly added under ice bath to 100ml, and stir 2 hours, hydrogen peroxide is finally added dropwise to molten
Liquid becomes clear, takes out carbon cloth and is washed with deionized water, and is dried in vacuo 12 hours.
Step 2): 0.01g (0.075mmol) 2- amino -5- sulfydryl -1,3,4- thiadiazoles, the 0.8ml concentrated sulfuric acid (96- are weighed
It 97wt%) is added in 150ml deionized water, ultrasonic 15min to whole dissolutions is then transferred into electrolytic cell and carries out voltolisation
It closes, 100 circle of polymerization, sweeping speed is 50mv/s, voltage range -0.2V -1.7V.Obtained product is placed after being washed with deionized water
It is 12 hours dry in 80 DEG C of vacuum ovens.
Step 3)；Organic polymer material is put into porcelain boat in high temperature process furnances to calcine, gas flow is 35ml min-1
Argon gas, be first warming up to 200 DEG C with 5 DEG C/min heating rate, keep the temperature 1 hour, then be warming up to 350 DEG C with 5 DEG C/min, heat preservation 2
Hour, be then warming up to 900 DEG C with 5 DEG C/min heating rate, keep the temperature 2 hours, last Temperature fall nitrogen sulphur codope
Self-supporting air electrode.
Embodiment 3
Step 1): cutting the carbon paper of one piece of 0.5x0.7cm, after being cleaned with deionized water, is then immersed in the concentrated sulfuric acid and dense nitre
(concentrated sulfuric acid 40ml, concentrated nitric acid 20ml) 30min in the mixed liquor of acid, then 6g potassium permanganate is added in mixed liquor and is stirred at room temperature
It mixes 1 hour, deionized water is then slowly added under ice bath to 100ml, and stir 2 hours, hydrogen peroxide is finally added dropwise to molten
Liquid becomes clear, takes out carbon paper and is washed with deionized water, and is dried in vacuo 12 hours.
Step 2): 0.005g (0.0375mmol) 2- amino -5- sulfydryl -1,3,4- thiadiazoles, the 0.8ml concentrated sulfuric acid are weighed
(96-97wt%) is added in 150ml deionized water, ultrasonic 15min to whole dissolutions, is then transferred into electrolytic cell and is carried out electricity
Polymerization, 100 circle of polymerization, sweeping speed is 50mv/s, voltage range -0.2V -1.7V.Obtained product is put after being washed with deionized water
It sets 12 hours dry in 80 DEG C of vacuum ovens.
Step 3)；Organic polymer material is put into porcelain boat in high temperature process furnances to calcine, gas flow is 35ml min-1
Argon gas, be first warming up to 200 DEG C with 5 DEG C/min heating rate, keep the temperature 1 hour, then be warming up to 350 DEG C with 5 DEG C/min, heat preservation 2
Hour, be then warming up to 900 DEG C with 5 DEG C/min heating rate, keep the temperature 2 hours, last Temperature fall nitrogen sulphur codope
Self-supporting air electrode.
Embodiment 4
Step 1): cutting the carbon cloth of one piece of 0.5x0.7cm, after being cleaned with deionized water, is then immersed in the concentrated sulfuric acid and dense nitre
(concentrated sulfuric acid 40ml, concentrated nitric acid 20ml) 30min in the mixed liquor of acid, then 6g potassium permanganate is added in mixed liquor and is stirred at room temperature
It mixes 1 hour, deionized water is then slowly added under ice bath to 100ml, and stir 2 hours, hydrogen peroxide is finally added dropwise to molten
Liquid becomes clear, takes out carbon cloth and is washed with deionized water, and is dried in vacuo 12 hours.
Step 2): 0.005g (0.0375mmol) 2- amino -5- sulfydryl -1,3,4- thiadiazoles, the 0.8ml concentrated sulfuric acid are weighed
(96-97wt%) is added in 150ml deionized water, ultrasonic 15min to whole dissolutions, is then transferred into electrolytic cell and is carried out electricity
Polymerization, 100 circle of polymerization, sweeping speed is 50mv/s, voltage range -0.2V -1.7V.Obtained product is put after being washed with deionized water
It sets 12 hours dry in 80 DEG C of vacuum ovens.
Step 3)；Organic polymer material is put into porcelain boat in high temperature process furnances to calcine, gas flow is 35ml min-1
Argon gas, be first warming up to 200 DEG C with 5 DEG C/min heating rate, keep the temperature 1 hour, then be warming up to 350 DEG C with 5 DEG C/min, heat preservation 2
Hour, be then warming up to 900 DEG C with 5 DEG C/min heating rate, keep the temperature 2 hours, last Temperature fall nitrogen sulphur codope
Self-supporting air electrode.
Claims (10)
1. a kind of preparation method of nonmetallic self-supporting air electrode, which comprises the following steps:
Step 1) is directly prepared using nitrogen source, sulphur source, carbon source containing nitrogen, sulphur, the equally distributed organic polymer of carbon；It weighs certain
Nitrogen source, sulphur source, the carbon source of amount are mixed and are scattered in solvent, then the mixed liquor is transferred in electrolytic cell and carries out polymerization reaction,
After a period of time, generates product and cleaned for several times with cleaning solution, it is dry to obtain carbon material and nitrogenous, the covalent organic polymer of sulphur electricity
Pole material；
The carbon material of synthesis and nitrogenous, the covalent organic polymer of sulphur electrode material are transferred in porcelain boat by step 2), and are put into
High temperature process furnances high temperature calcines certain time, it is made to be carbonized in inert gas, and natural cooling obtains nitrogen sulphur codope carbon
Base electrode.
2. a kind of preparation method of nonmetallic self-supporting air electrode described in accordance with the claim 1, which is characterized in that step
1), the sulfur-containing compound is 1,3,5- benzene, three thiophenol, trithiocyanuric acid, 2- amino -5- sulfydryl -1,3, one in 4- thiadiazoles
Kind is two or more；
Nitrogenous compound described in step 1) be triphosphazene, 2- amino -5- sulfydryl -1,3,4- thiadiazoles, melamine one
Kind is two or more.
3. a kind of preparation method of nonmetallic self-supporting air electrode described in accordance with the claim 1, which is characterized in that nitrogen source
It is same organic matter or two kinds of organic matters with sulphur source.
4. a kind of preparation method of nonmetallic self-supporting air electrode described in accordance with the claim 1, which is characterized in that step
1), the carbon compound is the one or more of carbon paper, carbon cloth.
5. a kind of preparation method of nonmetallic self-supporting air electrode described in accordance with the claim 1, which is characterized in that step
1), element sulphur in sulphur source, the ratio between amount of substance of carbon is 0.1-5:1.5:(50-100 in nitrogen and carbon source in nitrogen source).
6. a kind of preparation method of nonmetallic self-supporting air electrode according to claim 5, which is characterized in that sulphur source
The ratio between amount of substance of carbon preferably 1:1.5:(50-80 in nitrogen and carbon source in middle element sulphur, nitrogen source).
7. a kind of preparation method of nonmetallic self-supporting air electrode described in accordance with the claim 1, it is characterised in that 1), and electricity
Solving reactive polymeric temperature in slot is 20-25 DEG C；Polymerization time is 1-3 hours；Sweeping speed is 50mv/s, voltage range -0.2V -
1.7V。
8. a kind of preparation method of nonmetallic self-supporting air electrode described in accordance with the claim 1, which is characterized in that step
1) in drying steps, using vacuum drying, vacuum drying temperature is 65-150 DEG C, preferably 60-100 DEG C, more preferable 60-80
℃。
9. a kind of preparation method of nonmetallic self-supporting air electrode described in accordance with the claim 1, which is characterized in that step
2), inert protective gas used in the fumed pyrogenic process is high pure nitrogen, argon gas, purity >=99.99%；Step 2),
The pyrolytic process is warming up to 150-200 DEG C, preferably 200 DEG C with the rate of 1-10 DEG C/min, keeps the temperature 0.5-2.0 hours, and preferably 1
Hour, then 300-400 DEG C, preferably 350 DEG C are warming up to the rate of 1-10 DEG C/min, and 1-3.0 hours are kept the temperature, preferably 2 hours, most
800-1000 DEG C, preferably 900 DEG C are warming up to the rate of 1-10 DEG C/min again afterwards, keep the temperature 1-3.0 hours, preferably 2 hours.
10. the metal self-supporting air electrode being prepared according to the described in any item methods of claim 1-9.
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| CN112246289A (en) * | 2020-10-22 | 2021-01-22 | 哈尔滨工业大学 | Regeneration device and regeneration method for eliminating toxic influence of air impurities on oxygen electrode electrocatalyst |
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