CN109473686A - It is a kind of with biomass cotton be carbon-based catalyst and its preparation method and application - Google Patents
It is a kind of with biomass cotton be carbon-based catalyst and its preparation method and application Download PDFInfo
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- CN109473686A CN109473686A CN201811605493.6A CN201811605493A CN109473686A CN 109473686 A CN109473686 A CN 109473686A CN 201811605493 A CN201811605493 A CN 201811605493A CN 109473686 A CN109473686 A CN 109473686A
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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
- 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present embodiments relate to a kind of with biomass cotton for carbon-based catalyst and its preparation method and application, it is to form M-N-C active site by cotton, metal salt and nitrogen source for raw material, wherein cotton passes through metal salt, the doping of nitrogen source, pore-creating processing is bitten through ammonia quarter at high temperature, obtains the micron bar structure for being attached with nano-metal particle nano-pore.The catalyst has efficient, stable ORR catalytic activity, and low production cost is applied in metal-air battery, reduces battery cost, improves battery performance.
Description
Technical field
The present invention relates to metal-air battery technical field, more particularly, to it is a kind of with biomass cotton for carbon-based catalysis
Agent and its preparation method and application.
Background technique
Metal-air battery is a kind of electrochemical reaction appts, is electrolyte solution three by metal anode, air cathode
It is grouped as.The metal anode metal material more negative usually using electrode potential, such as magnalium zinc cadmium iron, metal anode is as combustion
Material, product cleanliness without any pollution, price are relatively cheap.Electrolyte solution is lye or neutral saline solutions.Air cathode is usually
Hydrophobic layer, current collector layer and catalytic active layer are constituted, directly using air in oxygen as oxidant.Relatively inexpensive combustion
Material, the price of air cathode often determine the cost of battery.However, Cathodic oxygen reduction (ORR) is urged in air cathode
Agent is then key, often determines battery performance.Therefore cheap, environmental protection is prepared, the cathode ORR catalyst of superior performance extremely closes
It is important.Currently, the ORR catalyst of business is Pt/C catalyst, but due to precious metals pt, fancy price causes nothing
Method is promoted the use of.In metal-air battery, can largely it be used to meet, and spending will not be too expensive, Many researchers
Using Mn base catalyst, however Mn base catalyst is in use, often its ORR catalytic performance is lower, far away from business Pt/C catalysis
Agent is also just restricted battery performance.
Such as, CN103877972 discloses a kind of raising MnOXThe method of catalyst, by MnOXIt carries out at electrochemistry
Reason increases the content of Mn (IV) in catalyst to improve the ORR performance of catalyst, however, its performance, no matter rise spike potential or
Half wave potential still has certain gap with respect to Pt/C.CN103682381 discloses a kind of nanometer or micron-sized LaNiO3Catalysis
Agent and MnO2The composite catalyst of catalyst, cheap, preparation is simple, industrial can amplify, and its ORR catalytic
Can: half wave potential -0.3V or so is relative to Hg/HgO, far away from business Pt/C.Then, honest and clean in the research of ORR catalyst
Valence can industrialize amplification preparation, and superior performance, it appears particularly important.
Although the understanding at present about the active site of ORR catalyst is not also overripened, however, base metal doping and
The composite material of the base metal M-N-C system of formation, it is considered to be most promising ORR catalyst material, such catalyst
The active sites of M-N structure are primarily formed, there is good catalytic activity.CN105375042 discloses that a kind of biomass is carbon-based to urge
Agent, biomass is carbon-based using biomass and metal salt as raw material, in metal development, by controlling not same amount metal salt
It is added, adjusts presoma mixed liquor composition and reaction temperature with the nitrogen treatment temperature that is carbonized and prepare pore structure and specific surface area
Controllable biomass carbon-supported catalysts.However, not having being directly added into for nitrogen source in the patented technology, it is living to form M-N-C
Property site ability is weaker, therefore in performance, no matter playing spike potential or half wave potential still has certain gap with respect to Pt/C
Or the catalytic activity similar to business Pt/C catalyst.In the patent with harder stalk be carbon-based raw material, raw material pre-treatment
Comparatively laborious, immersion absorbent solution effect is poor, and solution rests on macro surface more, and doping effect is bad, these are all influenced finally
Catalytic activity.Based on this, the present invention mainly selects common cheap cotton as carbon material, passes through more containing transition metal salt
And nitrogen source, the ORR catalyst of efficient stable is synthetically prepared out by microwave.
Summary of the invention
To solve the prior art, the purpose of the present invention is to provide a kind of with biomass cotton for carbon-based catalyst, should
Catalyst have efficient, stable ORR catalytic activity, low production cost, be applied to metal-air battery in, reduce battery at
This, improves battery performance.
Another goal of the invention of the present invention is to provide a kind of preparation method with biomass cotton for carbon-based catalyst, the party
Method is easy to operate, and is suitble to industrial amplification production.
The present invention is achieved through the following technical solutions:
It is a kind of with biomass cotton be carbon-based catalyst, be by cotton, metal salt and nitrogen source be raw material form M-N-C
Active site, the catalyst have the micron bar structure of nano-pore, are attached with metal nanoparticle on the nano-pore.
It is preferred that the present invention it is a kind of with biomass cotton be carbon-based catalyst, be by cotton, metal salt and nitrogen source for original
Material forms M-N-C active site, and wherein cotton passes through metal salt, and the doping of nitrogen source bites pore-creating processing through ammonia quarter at high temperature,
Obtain the micron bar structure for being attached with nano-metal particle nano-pore.
In above-mentioned catalyst, wherein cotton, metal salt, nitrogen source mass ratio be 1:(0.1-100): (0.1-100).It is excellent
Choosing, cotton, metal salt, nitrogen source mass ratio be 1:(0.1-10): (0.1-10).It is further preferred that cotton, metal salt, nitrogen source matter
Amount is than being 1:(0.1-5): (0.1-5).
Cotton of the present invention is micron club shaped structure, sees Fig. 1.
" M " of the present invention is metal.
Metal salt of the present invention is iron group salt, cobalt race salt, further preferably iron chloride, ferric nitrate, ferroheme, chlorination
It is one or more in cobalt, cobalt nitrate or cobalt acetate；More preferable metal salt is iron group and cobalt race according to mass ratio (1-3): (3-1) group
At.
The nitrogen source includes but is not limited to high molecular polymer, nitrogenous salt, nitrogenous gas, preferably poly m-phenylene diamine, chlorine
Change azanol, melamine, it is one or more in urea, ammonia.It is preferred that nitrogen source is high molecular polymer and nitrogenous salt quality ratio (1-
5): (5-1) composition.
Inert gas of the present invention includes but is not limited to nitrogen, argon gas, helium.It is preferred that nitrogen.
The present invention, in the case where special ratios are mutually added, realizes more doping gold by cotton, metal salt and nitrogen source at high temperature
Category source and nitrogen source reach synergistic effect, advantageously form M-N-C activity site.Activity can be increased to material pore-creating by being passed through ammonia
Site, while there are also the double effects of nitrating, to obtain the cheap M-N-C System Catalyst material of the present invention.
It is of the invention it is a kind of with biomass cotton be carbon-based catalyst preparation method, including using cotton as carrier and carbon
Source mixes nitrogen source, then mixes metal salt as base metal source, carries out high temperature cabonization, ammonia pore-creating processing in an inert atmosphere,
Obtain the catalyst material of M-N-C system.
It is of the invention it is a kind of with biomass cotton be carbon-based catalyst preparation method, include the following steps:
(1) it takes cotton to mix with stirring solvent, heat, taking out cotton, re-dry after cooling；
(2) metal salt is weighed, nitrogen source is configured to uniform mixed solution, spare；
(3) cotton for taking step (1) to dry is immersed in the mixed solution of step (2), freeze-drying；
(4) by the cotton after step (3) freeze-drying, in inert atmosphere, calcining is passed through ammonia, after completion of the reaction, cooling；
(5) by the product of step (4), ball milling adds strong acid pickling, dry, cooling；
(6) by the product after step (5) pickling, it is washed to neutrality, it is dry；
(7) product of step (6) is taken out, in an inert atmosphere, secondary clacining is cooling to get catalyst of the invention.
Solvent described in step (1) of the present invention is deionized water, ethyl alcohol, isopropanol, one or more of in ethylene glycol.It is excellent
Selecting the solvent is the mixed solution of water and ethyl alcohol, volume ratio 1:2-2:1, preferably 1:1.The cotton and solvent usage 1g cotton
Flower/5-30ml solvent.
It is heated to be 80-100 DEG C of heating 1-36 hours described in step (1).It is preferred that 80-100 DEG C heating 1-5 hours.
The preparation of metal salt and nitrogen source described in step (2) of the present invention, wherein metal salt is iron group, cobalt race salt etc., excellent
Select iron chloride, ferric nitrate, ferroheme, cobalt chloride, it is one or more in cobalt nitrate, cobalt acetate；The nitrogen source is high molecular polymerization
Object, nitrogenous salt, nitrogenous gas, preferably poly m-phenylene diamine, hydroxylamine chloride, melamine, it is one or more in urea, ammonia.
Step (3) of the present invention vacuum freezedrying 24-96 hours；Freeze-drying does not destroy material structure, keeps shape steady
It is fixed, the solution absorbed in cotton can be more solidificated in surface, be conducive to abundant combination when carbonization.And common drying side
Method does not have such advantage.
Inert atmosphere described in step (4) of the present invention includes but is not limited to nitrogen, argon gas, helium, preferably nitrogen.The present invention
Selected inert gas can prevent the entrance of oxygen when high temperature cabonization from material is reacted away.
It is calcined described in step (4) of the present invention, the preferably micro-wave oven 10-60 minutes calcining 0.1- risen in 800-1600 DEG C
It 8 hours, wherein the ammonia for being passed through 5-60 minutes at 400-600 DEG C is after completion of the reaction, cools down.Micro-wave oven acts the spy being rapidly heated
Point is beneficial to the formation of defect point, is more advantageous to form active site；It is passed through ammonia at high temperature, can be made to material
Hole increases active site, while there are also the double effects of nitrating, to obtain the cheap M-N-C System Catalyst material of the present invention
Material.
Strong acid described in step (5) of the present invention is one or more in nitric acid, hydrochloric acid or sulfuric acid.Pickling is extra in order to remove
The invalid metal of active sites is not participated in.
Calcining refers to 500-1600 DEG C secondary clacining 0.1-8 hours in tube furnace in step (7) of the present invention.Due to pickling
There is destruction to active site in the process, therefore secondary clacining mesh can be with reforming activity site.
Drying described in above-mentioned steps (1) of the present invention, (5)-(6) is placed in 60 DEG C -100 DEG C of baking oven dry.
Further preferably, the present invention it is a kind of with biomass cotton be carbon-based catalyst preparation method, including walk as follows
It is rapid:
(1) cotton is taken, the closed of the volume ratio 1:2-2:1 deionized water and alcohol mixed solution measured equipped with 5-30 times is put into
It in container, is heated 1-5 hours in 80 DEG C -100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be put into baking oven and do
It is dry；
(2) two or more metal salts are weighed and nitrogen source is configured to uniform mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument
In, vacuum freezedrying 36-72 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inert atmosphere, the 20-40 in micro-wave oven
Minute rises in calcining 0.1-1 hours of 1000-1200 DEG C, wherein being passed through 5-30 minutes ammonias at 400-600 DEG C, then
It is cooled to room temperature；
(5) product in step (4) is taken out from micro-wave oven, carries out ball milling 5-60 minutes, strong acid pickling is then added,
Be put into baking oven in 60-100 DEG C drying 1-24 hours, then cool to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3-6 times, until it is neutral, then in baking oven
Middle 60-100 DEG C of drying；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
Middle 500-1000 DEG C of secondary clacining 0.1-1 hours, then cools to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention.
Further preferably, the present invention it is a kind of with biomass cotton be carbon-based catalyst preparation method, including walk as follows
It is rapid:
(1) 24 parts of cotton are taken, is put into the closed container of the deionized water equipped with volume ratio 1:1 and alcohol mixed solution,
It is heated 2 hours in 100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) weigh 5.4 parts of iron chloride, 3.1 parts of cobalt chloride, 1.2 parts of poly m-phenylene diamine, 3.4 parts of hydroxylamine chloride be configured to
Even mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument
In, vacuum freezedrying 48 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inert atmosphere of nitrogen, 30 in micro-wave oven
Minute is risen in calcining 0.5 hour of 1200 DEG C, wherein being passed through 5 minutes ammonias at 500 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 30 minutes, strong acid pickling is then added, puts
Enter in baking oven and dried 6 hours at 80 DEG C, is then cooled to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3 times, until it is neutral, then in baking oven
80 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
In 900 DEG C secondary clacining 0.5 hour, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention.
The present invention also provides a kind of metal air battery cathodes, including above-mentioned catalyst, the metal-air battery includes
But it is not limited to aluminium-air cell, magnesium air battery, zinc-air battery.
Beneficial effect
1, the present invention for overcome existing metal air battery cathodes oxygen reduction catalyst preparation cost is high, catalytic activity is low,
And stability it is poor the disadvantages of, providing a kind of using common biomass cotton is raw material, passes through more doped metal salts and nitrogen source
Mode, the method that cheap, efficient, stable oxygen reduction catalyst is prepared by simple and quick method, and it is empty to be applied to metal
In pneumoelectric pond, battery cost is reduced, improves battery performance.
2, the raw materials used in the present invention price is low, and source is wide, and preparation method is simple, and the reaction time is short, easy to operate.Raw material is soft
Soft, immersion absorbent solution effect is good, and the solution absorbed in cotton can more be cured in surface, doping metals and nitrogen source effect
It is good；Metal salt used is less toxic, risk is small, very friendly to environment；Product cost obtained is lower, and catalytic activity is high, surely
The features such as qualitative good.
3, the structure of the raw material cotton used in the present invention is smooth micron club shaped structure (Fig. 1), through excessive metal salt, nitrogen
The doping in source bites pore-creating processing through ammonia quarter again at high temperature, obtains the micron bar structure (Fig. 2) of countless nano-pores.These are received
Metre hole provides more active sites for catalyst, and adheres to nano-metal particle, forms more M-N active sites, rodlike
Cotton on be etched out countless nanostructure aperture and adhere to many metal nanoparticles, to form M-N-C active sites
The composite catalyst of point, this M-N-C structure has higher ORR catalytic activity.Wherein biomass is cotton cheap and easy to get
Flower；More doping metals sources and nitrogen source, reach synergistic effect；Ammonia gas plays the double effects of pore-creating and nitrating；Micro-wave oven rises quick
The characteristics of heating, is beneficial to the formation of defect point, is more easily formed active site；Pickling in order to remove it is extra do not participate in
The invalid metal of active sites；Secondary clacining is for reforming activity position.
4, catalyst of the invention is applied in metal-air battery, greatly improves cell power density.It is specifically shown in examination
Example one is tested, the oxygen reduction catalyst that the present invention is prepared using cotton as raw material has very high half wave potential, reaches 0.893V, compare quotient
Industry Pt/C catalyst (0.868V) is higher by 25mV；Carrying current is also slightly above Pt/C；Meanwhile by the stability i-t of 24000s
Test, carrying current also only have 17.4% decaying, stable more than Pt/C catalyst (decaying 45.6%) more under equal conditions.
In addition, with this catalyst preparation at metal-air battery under 1V state power density be up to 286mW/cm2, normal better than at present
With MnO2For the battery performance (228mW/cm of the catalyst assembling of raw material preparation2).It is this directly commonly honest and clean using market
The method of valence article prepared catalyst provides a novel thinking in the preparation of cell cathode catalyst.
Detailed description of the invention:
Fig. 1 is the scanning electron microscope (SEM) photograph of cotton structure, it can be seen that cotton is micron club shaped structure；
Fig. 2 is the scanning electron microscope (SEM) photograph of the catalyst of cotton raw material preparation, and be etched out countless receive on rodlike cotton
Rice structure aperture simultaneously adheres to many metal nanoparticles；
Fig. 3 is that the electro catalytic activity of prepared cotton and business Pt/C catalyst compares figure.It can be seen that prepared urge
The catalytic activity of agent is higher than business Pt/C；
Fig. 4 is the stability test figure of prepared cotton and business Pt/C catalyst.It can be seen that prepared catalyst
Stability is much higher than Pt/C；
Fig. 5 is prepared cotton catalyst and MnO2Catalyst assembles the polarization curve after aluminum-air battery.It can see
After made cotton catalyst is equipped to aluminium-air cell out, the power density under 1V state is much higher than MnO2Power density.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in the embodiment of the present invention
Technical solution is clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than complete
The embodiment in portion.Based on the embodiments of the present invention, those of ordinary skill in the art are without creative efforts
Every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise entire
In specification and claims, the term " include " or its transformations will be understood as be include institute
The element or component of statement, and do not exclude other elements or other components.
Embodiment 1
(1) cotton 24g is taken, is put into (ratio 1:1) closed container equipped with deionized water and alcohol mixed solution,
It is heated 2 hours in 100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) iron chloride 5.4g, cobalt chloride 3.1g, poly m-phenylene diamine 1.2g, hydroxylamine chloride 3.4g is weighed to be configured to uniformly
Mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument
In, vacuum freezedrying 48 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inertia N2In gas atmosphere, 30 in micro-wave oven
Minute is risen in calcining 0.5 hour of 1200 DEG C, wherein being passed through 5 minutes ammonias at 500 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 30 minutes, strong acid pickling is then added, puts
Enter in baking oven and dried 6 hours at 80 DEG C, is then cooled to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3 times, until it is neutral, then in baking oven
80 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
In 900 DEG C secondary clacining 0.5 hour, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention；
(9) catalyst in (8) is used to prepare air cathode, is assembled into aluminium-air cell, be passed through the progress of 4M KOH solution
Battery performance test.
Embodiment 2
(1) cotton 24g is taken, (ratio 1:1) closed container for measuring deionized water and alcohol mixed solution equipped with 10 times is put into
In, it is heated 5 hours in 80 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) iron chloride 5.4g, cobalt chloride 3.1g, poly m-phenylene diamine 1.2g, hydroxylamine chloride 3.4g is weighed to be configured to uniformly
Mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument
In, vacuum freezedrying 36 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inert argon atmosphere, 20 in micro-wave oven
Minute is risen in calcining 1 hour of 1000 DEG C, wherein being passed through 10 minutes ammonias at 400 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 20 minutes, strong acid pickling is then added, puts
Enter in baking oven and dried 10 hours at 60 DEG C, is then cooled to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 4 times, until it is neutral, then in baking oven
60 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
In 500 DEG C secondary clacining 1 hour, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention.
Embodiment 3
(1) cotton 24g is taken, (ratio 2:1) closed container that 5 times of amounts are equipped with deionized water and alcohol mixed solution is put into
In, it is heated 2 hours in 100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) iron chloride 5.4g, cobalt chloride 3.1g, poly m-phenylene diamine 1.2g, hydroxylamine chloride 3.4g is weighed to be configured to uniformly
Mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument
In, vacuum freezedrying 72 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inertia N2 gas atmosphere, 40 in micro-wave oven
Minute is risen in calcining 0.1 hour of 1200 DEG C, wherein being passed through 5 minutes ammonias at 600 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 40 minutes, strong acid pickling is then added, puts
Enter in baking oven and dried 1 hour at 100 DEG C, is then cooled to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3 times, until it is neutral, then in baking oven
100 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
In 1000 DEG C secondary clacining 0.1 hour, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention.
Embodiment 4
(1) cotton 16g is taken, (ratio 1:1) closed container for measuring deionized water and alcohol mixed solution equipped with 30 times is put into
In, it is heated 2 hours in 100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) iron chloride 5g, cobalt chloride 5g, poly m-phenylene diamine 3g, hydroxylamine chloride 3g are weighed, is configured to uniformly mix molten
Liquid；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument
In, vacuum freezedrying 48 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inertia N2 gas atmosphere, 30 in micro-wave oven
Minute is risen in calcining 0.5 hour of 1200 DEG C, wherein being passed through 5 minutes ammonias at 500 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 30 minutes, strong acid pickling is then added, puts
Enter in baking oven and dried 6 hours at 80 DEG C, is then cooled to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3 times, until it is neutral, then in baking oven
80 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
In 900 DEG C secondary clacining 0.5 hour, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention.
Embodiment 5
(1) cotton 2.8g is taken, (ratio 1:1) closed container for measuring deionized water and alcohol mixed solution equipped with 5 times is put into
In, it is heated 2 hours in 100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) ferric nitrate 6g, cobalt nitrate 2g, melamine 1g, urea 5g are weighed and is configured to uniform mixed solution；(3) claim
It takes the cotton of step (1) dried to be immersed in the mixed solution in step (2), places into freeze-drying instrument, freezing vacuum is dry
Dry 48 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inertia N2 gas atmosphere, 30 in micro-wave oven
Minute is risen in calcining 0.5 hour of 1200 DEG C, wherein being passed through 5 minutes ammonias at 500 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 30 minutes, strong acid pickling is then added, puts
Enter in baking oven and dried 6 hours at 80 DEG C, is then cooled to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3 times, until it is neutral, then in baking oven
80 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
In 900 DEG C secondary clacining 0.5 hour, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention.
Embodiment 6
(1) cotton 130g is taken, (ratio 1:2) closed container for measuring deionized water and alcohol mixed solution equipped with 10 times is put into
In, it is heated 36 hours in 100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) ferroheme 5g, cobalt acetate 3g, poly m-phenylene diamine 2g, hydroxylamine chloride 3g are weighed and is configured to uniform mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument
In, vacuum freezedrying 96 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inertia N2 gas atmosphere, 60 in micro-wave oven
Minute is risen in calcining 8 hours of 1600 DEG C, wherein being passed through 60 minutes ammonias at 500 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 60 minutes, strong acid pickling is then added, puts
Enter in baking oven and dried 24 hours at 80 DEG C, is then cooled to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 6 times, until it is neutral, then in baking oven
80 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
In 1600 DEG C secondary clacining 8 hours, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention.
Embodiment 7
(1) cotton 1.2g is taken, is put into (ratio 1:1) closed container equipped with deionized water and alcohol mixed solution,
It is heated 1 hour in 100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) iron chloride 5g, cobalt chloride 3g, poly m-phenylene diamine 1g, hydroxylamine chloride 3g are weighed and is configured to uniform mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument
In, vacuum freezedrying 24 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inertia N2 gas atmosphere, 30 in micro-wave oven
Minute is risen in calcining 0.1 hour of 500 DEG C, wherein being passed through 5 minutes ammonias at 400 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 30 minutes, strong acid pickling is then added, puts
Enter in baking oven and dried 1 hour at 80 DEG C, is then cooled to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3 times, until it is neutral, then in baking oven
80 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
In 500 DEG C secondary clacining 0.1 hour, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention；
Embodiment 8
(1) cotton 2.4g is taken, is put into (ratio 1:1) closed container equipped with deionized water and alcohol mixed solution,
It is heated 2 hours in 100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) iron chloride 5g, cobalt chloride 3g, poly m-phenylene diamine 1g, hydroxylamine chloride 3g are weighed and is configured to uniform mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument
In, vacuum freezedrying 48 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inertia N2 gas atmosphere, 30 in micro-wave oven
Minute is risen in calcining 0.3 hour of 1200 DEG C, wherein being passed through 5 minutes ammonias at 500 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 30 minutes, strong acid pickling is then added, puts
Enter in baking oven and dried 2 hours at 80 DEG C, is then cooled to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3 times, until it is neutral, then in baking oven
80 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
In 900 DEG C secondary clacining 0.3 hour, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention；
One catalyst activity of test example and stability
The oxygen reduction catalyst (such as embodiment 1) that the present invention is prepared using cotton as raw material has very high half wave potential, reaches
0.893V is higher by 25mV than business Pt/C catalyst (0.868V)；Carrying current is also slightly above Pt/C；Meanwhile by 24000s
Stability i-t test, carrying current also only has 17.4% decaying, more than (the decaying of Pt/C catalyst under equal conditions
45.6%) stable more.In addition, with this catalyst preparation at metal-air battery under 1V state power density be up to
286mW/cm2, better than currently used with MnO2For the battery performance (228mW/cm of the catalyst assembling of raw material preparation2).See figure
3-5.The synergy of the two more more nitrogen sources of metal of the present invention of test example
The present invention: embodiment 1
Control group 1: step (2) weighs iron chloride 8.4g and is configured to uniform solution；Other steps according to embodiment 1 behaviour
Make.
Control group 2: step (2) weighs iron chloride 8.4g, poly m-phenylene diamine 4.6g is configured to uniform mixed solution；It is other
Step according to embodiment 1 operation.
Method: the catalyst of catalyst and control group 1,2 of the invention is subjected to the test of ORR electrocatalysis characteristic.
As a result: being shown in Table 1, when the monometallic of control group 1 adulterates, performance half wave potential only has 0.72V or so, control group 2
When monometallic sole nitrogen source, 0.84V or so can achieve, the more nitrogen sources of more metals of the invention are up to 0.893V and are catalyzed than business Pt/C
Agent (0.868V).As it can be seen that the more nitrogen sources of more metals of the invention just have synergistic effect to catalyst activity is improved.
The ORR electrocatalysis characteristic of the more nitrogen sources of more than 1 metal of table acts synergistically
Claims (10)
1. it is a kind of with biomass cotton be carbon-based catalyst, be by cotton, metal salt and nitrogen source be raw material is formed M-N-C work
Property site, the catalyst has the micron bar structure of nano-pore, is attached with metal nanoparticle on the nano-pore；It is preferred that
It is a kind of with biomass cotton be carbon-based catalyst, be by cotton, metal salt and nitrogen source be raw material form M-N-C active sites
Point, wherein cotton passes through metal salt, and the doping of nitrogen source bites pore-creating processing through ammonia quarter at high temperature, obtains being attached with nanogold
The micron bar structure of metal particles nano-pore.
2. catalyst as described in claim 1, which is characterized in that the raw material of the catalyst is by cotton, metal salt, nitrogen source
Mass ratio be 1:(0.1-100): (0.1-100) composition；It is preferred that the raw material of the catalyst is by cotton, metal salt, nitrogen source
Mass ratio be 1:(0.1-10): (0.1-10) composition；It is further preferred that the raw material of the catalyst is by cotton, metal salt, nitrogen source
Mass ratio be 1:(0.1-5): (0.1-5)) composition.
3. catalyst as described in claim 1, it is characterised in that: the metal salt is iron group salt, cobalt race salt；Nitrogen source is high score
Sub- polymer, nitrogenous salt, nitrogenous gas；It is preferred that the metal salt is iron group salt, cobalt race salt according to mass ratio (1-3):
(3-1) composition；The nitrogen source is high molecular polymer and nitrogenous salt quality ratio (1-5): (5-1) is formed.
4. catalyst as claimed in claim 3, which is characterized in that the metal salt is iron chloride, ferric nitrate, ferroheme, chlorine
Change cobalt, cobalt nitrate, one or more in cobalt acetate；The nitrogen source is poly m-phenylene diamine, hydroxylamine chloride, melamine, urea, ammonia
It is one or more in gas.
5. it is a kind of with biomass cotton be carbon-based catalyst preparation method, which is characterized in that including using cotton be carrier with
Carbon source mixes nitrogen source, then mixes metal salt as base metal source, in an inert atmosphere progress high temperature cabonization, at ammonia pore-creating
Reason, obtains the catalyst material of M-N-C system.
6. preparation method as claimed in claim 5, which comprises the steps of:
(1) it takes cotton to mix with stirring solvent, heat, taking out cotton, re-dry after cooling；
(2) metal salt is weighed, nitrogen source is configured to uniform mixed solution, spare；
(3) cotton for taking step (1) to dry is immersed in the mixed solution of step (2), freeze-drying；
(4) by the cotton after step (3) freeze-drying, in inert atmosphere, calcining is passed through ammonia, after completion of the reaction, cooling；
(5) by the product of step (4), ball milling adds strong acid pickling, dry, cooling；
(6) by the product after step (5) pickling, it is washed to neutrality, it is dry；
(7) product of step (6) is taken out, in an inert atmosphere, secondary clacining is cooling to get catalyst of the invention.
7. preparation method as claimed in claim 6, it is characterised in that: be heated to be 80-100 DEG C of heating 1- described in step (1)
36 hours.It is preferred that 80-100 DEG C heating 1-5 hours；Step (3) vacuum freezedrying 24-96 hours.
8. preparation method as claimed in claim 6, it is characterised in that: step (4) calcining is at micro-wave oven 10-60 minutes
It is risen in calcining 0.1-8 hours of 800-1600 DEG C, wherein being passed through 5-60 minutes ammonia end of reaction at 400-600 DEG C
Afterwards, cooling；Calcining refers to 500-1600 DEG C secondary clacining 0.1-8 hours in tube furnace in step (7).
9. preparation method as claimed in claim 6, which comprises the steps of:
(1) cotton is taken, the closed container of the volume ratio 1:2-2:1 deionized water and alcohol mixed solution measured equipped with 5-30 times is put into
In, it is heated 1-5 hours in 80 DEG C -100 DEG C of baking oven, after being cooled to room temperature, takes out cotton, be placed in oven and dried；
(2) two or more metal salts are weighed and nitrogen source is configured to uniform mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument, cold
Freeze vacuum drying 36-72 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inert atmosphere, 20-40 minutes in micro-wave oven
It is risen in calcining 0.1-1 hours of 1000-1200 DEG C, wherein being passed through 5-30 minutes ammonias at 400-600 DEG C, is then cooled down
To room temperature；
(5) product in step (4) is taken out from micro-wave oven, carries out ball milling 5-60 minutes, strong acid pickling is then added, is put into
In baking oven in 60-100 DEG C drying 1-24 hours, then cool to room temperature；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3-6 times, until neutral, the then 60- in baking oven
100 DEG C of dryings；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
500-1000 DEG C secondary clacining 0.1-1 hours, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention；
It is preferred that it is a kind of with biomass cotton be carbon-based catalyst preparation method, include the following steps:
(1) 24 parts of cotton are taken, is put into the closed container of the deionized water equipped with volume ratio 1:1 and alcohol mixed solution, 100
DEG C baking oven in heat 2 hours, after being cooled to room temperature, take out cotton, be placed in oven and dried；
(2) weigh 5.4 parts of iron chloride, 3.1 parts of cobalt chloride, 1.2 parts of poly m-phenylene diamine, 3.4 parts of hydroxylamine chloride be configured to it is uniform
Mixed solution；
(3) cotton dried for weighing step (1) is immersed in the mixed solution in step (2), places into freeze-drying instrument, cold
Freeze vacuum drying 48 hours；
(4) cotton that will be lyophilized in step (3), is put into porcelain boat, in inert atmosphere of nitrogen, 30 minutes in micro-wave oven
It is risen in calcining 0.5 hour of 1200 DEG C, wherein being passed through 5 minutes ammonias at 500 DEG C, is then cooled to room temperature；
(5) product in step (4) is taken out from tube furnace, carries out ball milling 30 minutes, strong acid pickling is then added, is put into baking
It dries 6 hours, then cools to room temperature at 80 DEG C in case；
(6) by the product after pickling in step (5), with deionized water eccentric cleaning 3 times, until it is neutral, then 80 DEG C in baking oven
It is dry；
(7) product completed dry in step (6) is taken out, is placed again into porcelain boat, in an inert atmosphere, in tube furnace
900 DEG C secondary clacining 0.5 hour, then cool to room temperature；
(8) product in step (7) is taken out to get catalyst of the invention.
10. a kind of metal air battery cathodes, which is characterized in that including catalyst described in claim 1-4 any one, institute
Stating metal-air battery is aluminium-air cell, magnesium air battery, zinc-air battery.
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