CN105304913A - Nitrogen/transition metal-codoped hierarchical-pore carbon oxygen reduction catalyst, and preparation method and application thereof - Google Patents
Nitrogen/transition metal-codoped hierarchical-pore carbon oxygen reduction catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nitrogen/transition metal-codoped hierarchical-pore carbon oxygen reduction catalyst, and a preparation method and application thereof. The catalyst comprises the following raw materials by mass: 10 to 60% of a template, 5 to 60% of a nitrogen-containing polymer and 15 to 40% of a transition metal salt. The method comprises the following steps: separately dissolving the nitrogen-containing polymer, the template and the transition metal salt in solvents to obtain a nitrogen-containing polymer solution, a template solution and a transition metal salt solution respectively; subjecting the three solutions to mixing under stirring and to drying so as to obtain a precursor; roasting the precursor so as to obtain a catalyst intermediate; and subjecting the catalyst intermediate to alkali washing, acid pickling and roasting again so as to obtain the catalyst. The preparation method is simple to operate, has low cost and high yield and greatly reduces dependence on the precious metal Pt; and the prepared catalyst overcomes the problem of corrosion caused by usage of a non-noble metal catalyst and has wide application prospects in the aspects of a metal-air battery and a flow battery.
Description
Technical field
The invention belongs to oxygen reduction catalyst field, particularly a kind of nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst and its preparation method and application.
Background technology
Under the overall background that the fossil energy such as Global Oil, coal reserves constantly reduce and the environmental pollution that causes is day by day serious, utilize the high efficiency energy memory device of electrochemical reaction to be subject to people and greatly pay close attention to [NanoLett.2012,12,1946-1952].Metal-air cell is just used for railway, the postal system as compact power in the World War I.It is a kind of between primary cell and fuel cell " half fuel " battery, have the feature of fuel cell and battery concurrently.Positive pole due to zinc-air cell is from the oxygen in air, and using it as positive active material, is thus really deserved to be called a kind of efficient green battery with benefiting environment-friendly type.Zinc-air cell has high current density (generally more than 340KWh/Kg, common lead acid accumulator also can only be in the scope of 20 1 50Kwh/Kg), the advantage such as production cost is low, abundant raw materials is easy to get, structure is simple, it is easy to manufacture, discharge stability, it is a kind of power supply with great market prospect, be acknowledged as one of 21 century the most effective and reliable new energy technology [Nanoscale2013,5,4657-4661].In addition, metal-air cell theoretical energy density (1084Wh/Kg), far above traditional lithium ion battery (being 4-5 times of lithium ion battery energy density).And as the selection of raw material, zinc is the 4th metal the abundantest in the earth's crust, can bear larger battery production to meet ever-increasing demand, oxygen is present in again in air widely simultaneously.But electrocatalytic oxidation reduction reaction (ORR) dynamics process slowly on negative electrode, limits the efficiency of metal-air battery.The catalyst being used as oxygen electrode at present mainly contains noble metal and alloy thereof, and as Pt, Ag and Pt alloy etc., the noble metal catalysts such as platinum carbon are still counted as ORR the highest active eelctro-catalyst.But the noble metal catalyst preparation costs such as platinum are high, stability is poor, and the problem that earth reserves are rare simultaneously limits the scale application of air electrode.In zinc-air cell, improve the catalytic performance of oxygen electrode, find the focus that the catalyst of Cheap highly effective is zinc and air cell research.
In recent years, researcher is devoted to the research of non-precious metal catalyst, to fundamentally solving catalyst cost to the business-like impact of metal-air battery.Along with the fast development of electro-catalysis technology, a kind of material of main part that material with carbon element is applied as it, in academia and industrial quarters by extensive concern.Generally believe, high-specific surface area, high porosity and suitable pore structure are conducive to promoting the mass transfer such as oxygen, and then improve the catalytic activity of catalyst.Template because of can obtain controlled architecture, specific morphology material with carbon element and be widely used in electrochemical field.According to report, for N doping gold/mesoporous carbon catalyst, there is in alkaline medium good chemical property by die version legal system, but there is preparation method's complexity in such catalyst, conditional request is harsh, yield poorly, be unsuitable for the defects such as suitability for industrialized production, no matter be all need to improve [Appl.Catal.B:Environ.127,300 (2012)] in chemical property or stability etc.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst and its preparation method and application, the method easily operates, cost is low, productive rate high, greatly reduce the dependence to precious metals pt, the etching problem that the use overcoming non-precious metal catalyst brings.The catalyst that the method prepares has efficient hydrogen reduction performance in atmosphere, is the good air electrode catalyst that can apply to the metal-air cell fields such as zinc-sky, aluminium-sky and magnesium-sky.
A kind of nitrogen of the present invention/transition metal codope multi-stage porous carbon oxygen reduction catalyst, the raw material of described catalyst comprises: mass content be 10 ~ 60% template, mass content be 5 ~ 60% nitrogenous high polymer and mass content be the transition metal salt of 15 ~ 40%.
Described template is the colloid of the powder of silicon dioxide, the aqueous solution of silicon dioxide, the ethanolic solution of silicon dioxide or silicon dioxide; Wherein, the diameier of silicon dioxide is 5 ~ 1000nm.
Described nitrogenous high polymer is polyquaternary amine [two (2-chloroethyl) ether-alt-1, two [3-(dimethylamino) propyl group] urea of 3-], the polymer of chlorination-1-vinyl-3-methyl isophthalic acid H-imidazoles and l-vinyl-2-pyrrolidone, at least one in poly-(diallyldimethylammonium chloride) and propenyl dimethyl ammonium chloride-acrylamide.
Described transition metal salt is at least one in ferrous sulfate, cobaltous sulfate, nickelous sulfate and frerrous chloride.
The preparation method of a kind of nitrogen of the present invention/transition metal codope multi-stage porous carbon oxygen reduction catalyst, comprising:
(1) nitrogenous high polymer, template and transition metal salt are dissolved in respectively in solvent, the nitrogenous high polymeric solution obtained, template solution and transition metal salting liquid mix under agitation, dry, obtain presoma; Wherein, presoma comprise mass content be 10 ~ 60% template, mass content be 5 ~ 60% nitrogenous high polymer and mass content be the transition metal salt of 15 ~ 40%, mass content with the gross mass of presoma for benchmark;
(2) presoma in step (1) is warming up to 700 ~ 1000 DEG C of roasting 2 ~ 4h under inert gas atmosphere protection, obtains catalyst intermediate;
(3) by catalyst intermediate alkali cleaning process 48 ~ 72h in step (2), cleaning, dry, obtain a nitrogen/transition metal codope multi-stage porous carbon material;
(4) by nitrogen/transition metal codope multi-stage porous carbon material 60 ~ 85 DEG C of pickling processes 10 ~ 24h in step (3); suction filtration, cleaning; dry; and 700 ~ 1000 DEG C of roasting 1 ~ 2h are warming up under inert gas atmosphere protection, obtain nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst.
In described step (1), the mass fraction of nitrogenous high polymeric solution is 5% ~ 60%; The mass fraction of template solution is 10% ~ 60%; The mass fraction of transition metal salting liquid is 15% ~ 40%.
In described step (1), solvent is hydrochloric acid; Dry temperature is 50 ~ 90 DEG C.
Described step (2) and the middle inert gas of step (4) are nitrogen.
In described step (2), catalyst intermediate is the catalyst intermediate after carbonization.
Alkali cleaning is treated to the alkali cleaning at room temperature ~ 60 DEG C of excessive sodium hydroxide solution in described step (3).
The mass fraction of described sodium hydroxide solution is 12%.
Clean as washed with de-ionized water in described step (3) and step (4).
In described step (4), pickling processes is excessive sulfuric acid treatment.
The concentration of described sulfuric acid is 0.5 ~ 1M.
The application of a burst of nitrogen of the present invention/transition metal codope multi-stage porous carbon oxygen reduction catalyst, described nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst is applied to the air electrode preparing metal-air cell.
Described metal-air cell is zinc-empty battery, aluminium-empty battery or magnesium-empty battery.
The preparation method of described air electrode comprises: isopropyl alcohol and Nafion solution are obtained mixed solution according to volume ratio 5:1 ~ 3:1, by nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst is distributed in mixed solution, ultrasonic, be sprayed in gas-diffusion electrode, drying, obtains air electrode.
The mass concentration of described Nafion solution is 0.5 ~ 1%.
The catalyst loading of described gas-diffusion electrode is 0.5 ~ 5mg/cm
2.
Described gas-diffusion electrode is carbon paper, carbon felt, carbon cloth, foam Ni or stainless (steel) wire.
Described air electrode should be the zinc-empty monocell performance test for reality, and have certain difference with glass disc electrode, glass disc electrode is applied to three-electrode system, carries out half-cell performance test and sign to catalyst.
The described ultrasonic time is 20 ~ 60min.
The present invention using polymer with nitrogen as carbon, nitrogen presoma, slaine green vitriol is as Fe source, nano silicon is as template, select NaOH to remove template silicon dioxide simultaneously, not only preparation method is simple, and environmentally friendly, special productive rate significantly increases, and is easy to suitability for industrialized production.
Preparation method of the present invention is simple, easy operation, cost are low, and productive rate high, greatly reduces the dependence to precious metals pt, the etching problem that the use overcoming non-precious metal catalyst brings, prepared catalyst has efficient hydrogen reduction performance in atmosphere.Utilize the air electrode of catalyst preparing of the present invention in Zn-air cell, have excellent discharge performance and stability, metal-air cell and flow battery are had broad application prospects.
beneficial effect
(1) doping multi-stage porous carbon oxygen reduction catalyst of the present invention shows excellent chemical property, and the catalyst ORR that at 800 DEG C, preparation table reveals plays spike potential at 0.98V, and assembling metal air monocell, wherein cathod catalyst carrying capacity is 3mg/cm
2time, under natural air, energy output is up to 530mW/cm
2;
(2) after the air electrode that prepared by doping multi-stage porous carbon oxygen reduction catalyst of the present invention, in small area analysis discharge and recharge, continuous constant-current discharge is not significantly decayed for 100 hours, also excellent stability is had in high current charge-discharge, can metal-air battery be directly used in, significantly reduce the cost of manufacture of metal-air cell;
(3) the present invention adopts template, and that obtained catalyst has high-ratio surface sum is micro--and be situated between-large hierarchical porous structure, and the transmission of the materials such as oxygen is greatly improved;
(4) the present invention with cheap nitrogenous high polymer be carbon source, nitrogenous source, a certain amount of transition metal salt of compound, under an inert atmosphere through twice carbonization, a pickling and an alkali cleaning, adopt template to obtain the doping multi-stage porous carbon catalyst with high catalytic activity and stability; Preparation method is simple, and easily operation, cost are low, productive rate high; The catalyst prepared greatly reduces the dependence to precious metals pt, the etching problem that the use overcoming non-precious metal catalyst brings, and is the good air electrode catalyst that can apply to the metal-air cell fields such as zinc-sky, aluminium-sky and magnesium-sky.
Accompanying drawing explanation
Fig. 1 is multi-stage porous carbon catalyst n-Fe-HPC, N-Ni-HPC, N-Co-HPC cyclic voltammetry curve figure under oxygen and condition of nitrogen gas that adulterates in embodiment 1;
Fig. 2 is the ORR polarization curve comparison diagram of multi-stage porous carbon catalyst n-Fe-HPC, N-Ni-HPC, N-Co-HPC and 20%Pt/C of adulterating in embodiment 2;
Fig. 3 is that in embodiment 3, N-Fe-HPC makes air electrode, and carrying capacity is respectively 1.0,2.0 and 3.0mg/cm
2at the generating curve chart of Metal Zn-air primary cell;
Fig. 4 is after in embodiment 4, N-Fe-HPC is prepared into air electrode, respectively at electric current 10mA/cm
2and 100mA/cm
2under constant-current discharge figure;
Fig. 5 for being after in embodiment 5, N-Fe-HPC is prepared into air electrode, at 10mA/cm
2under, after long-time constant-current discharge, change alkali lye and zine plate, the open circuit voltage resolution chart of battery.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
A kind of nitrogen/M (M=Fe/Co/Ni) codope multi-stage porous carbon catalyst, obtain by presoma is carried out process, described presoma comprise mass content be 20% SiO 2 powder, mass content be 25% nitrogenous high polymer [polyquaternary amine (two (2-chloroethyl) ether-alt-1, two [3-(dimethylamino) propyl group] urea of 3-(being called for short: PQ-2, Sigmaaldrich company) and mass content are the slaine (FeSO of 55%
4, CoSO
4, NiSO
4).Above-mentioned mass content with the gross mass of presoma for benchmark.Described process comprises first time roasting reduction process, alkali cleaning process, pickling processes and the process of second time roasting reduction.
The preparation method of described nitrogen/M codope multi-stage porous carbon oxygen reduction catalyst is:
(1) by PQ-2, to be 500nm SiO 2 powder and transition metal salt be configured to mass fraction with the hydrochloric acid of 1 mole often liter to particle diameter is respectively respectively the PQ-2 solution of 5%, the SiO of 10%
2solution and 40% transition metal salt solution, take the transition metal salt solution of 34.38g40%, the PQ-2 solution of 125g5% and the SiO of 50g10%
2solution is mixed directly under agitation, after spend the night in 85 DEG C of baking oven inner dryings, and pulverize, obtains catalyst precursor.
(2) above-mentioned presoma is placed in quartz boat, at N
2be increased to roasting reduction process 90min under 800 DEG C of conditions with 10 DEG C/min heating rate under atmosphere protection, obtain the catalyst intermediate after carbonization.
(3) by the catalyst intermediate after carbonization with excessive mass fraction be 12% NaOH solution alkali cleaning 48h at 60 DEG C, dry after suction filtration, washed with de-ionized water, obtain a nitrogen/M codope multi-stage porous carbon material.
(4) by above-mentioned nitrogen/M (M=Fe/Co/Ni) codope multi-stage porous carbon material by excessive concentration be sulfuric acid pickling processes 10h at 85 DEG C of 0.5M; dry after the cleaning of suction filtration, deionization; and again under inert gas atmosphere protection, be warming up to 800 DEG C of roasting reduction process 90min, obtain doping multi-stage porous carbon catalyst n-Fe-HPC, N-Ni-HPC, N-Co-HPC.
The cyclic voltammetry curve of catalyst is measured with electrochemical workstation.Oxygen is passed into 30 minutes at the potassium hydroxide solution of 0.1mol/L, again the glass disc electrode scribbling catalyst is made work electrode, full calomel electrode and Pt electrode is respectively reference electrode and to electrode, measure the cyclic voltammetry curve of N-Fe-HPC, N-Ni-HPC, N-Co-HPC catalyst successively at three-electrode system.
As shown in Figure 1, above catalyst has obvious hydrogen reduction peak to experimental result, and wherein N-Fe-HPC spike potential reaches 0.83V, and peak current then reaches 2.81mA/cm
2.
Embodiment 2
The Nafion solution being 0.5% by isopropyl alcohol and mass concentration mixes according to volume ratio 4:1, obtain the mixed solution of isopropyl alcohol and Nafion, the embodiment 1 gained nitrogen/M codope multi-stage porous carbon catalyst of 2mg and 20%Pt/C catalyst are distributed in the mixed solution of above-mentioned 0.6ml isopropyl alcohol and Nafion, under ultrasonication, obtain homogeneous catalyst agent solution.Then drip and be coated onto on glass disc electrode, make catalyst n-Fe-HPC respectively, the carrying capacity of N-Ni-HPC, N-Co-HPC is 500 μ g/cm
2, the carrying capacity of 20%Pt/C catalyst is 100 μ g/cm
2, naturally dry.Oxygen is passed into 30 minutes at electrolyte solution, to the glass carbon disk electrode of catalyst be scribbled as work electrode again, full calomel electrode and Pt electrode is respectively reference electrode and to electrode, measure the polarization curve of N-Fe-HPC, N-Ni-HPC, N-Co-HPC and 20%Pt/C catalyst under alkaline medium 0.1mol/LKOH successively in three-electrode system.
As shown in Figure 2, prepared multi-stage porous carbon catalyst all shows excellent hydrogen reduction catalytic performance to experimental result, and wherein the hydrogen reduction performance of N-Fe-HPC catalyst is the most obvious, and the spike potential that rises of ORR reaches 0.98V.When 0.8V, the current density of N-Fe-HPC catalyst is 5.7mA/cm
2, be much better than 20%Pt/C catalyst.
Embodiment 3
The Nafion solution being 0.5% by isopropyl alcohol and mass concentration mixes according to volume ratio 3:1, obtain the mixed solution of isopropyl alcohol and Nafion, the embodiment 1 gained N-Fe-HPC catalyst of 10mg is distributed in the mixed solution of above-mentioned 12ml isopropyl alcohol and Nafion, under ultrasonication, obtains homogeneous catalyst agent solution.Then be sprayed on the carbon paper of hydrophobic treatment that (carrying capacity is 1.0,2.0,3.0mg/cm
2), 60 DEG C of dryings prepare air electrode in 30 minutes, simultaneously using the zinc paper tinsel identical with carbon paper area as negative electrode, potassium hydroxide solution reaction cell groove air electrode, zinc paper tinsel being put into 6mol/L forms actual two electrode zinc-empty battery, activation of fuel cell system is utilized to utilize gradual change current-mode to test: normal temperature and pressure, test generating curve and polarization curve.
As shown in Figure 3, along with the increase of carrying capacity, power generation performance is significantly improved, when carrying capacity is 3.0mg/cm
2time, monocell open circuit voltage can reach 1415mV, and maximum generation power density reaches 536mW/cm
2.When voltage is 1V, electric current reaches 317mA/cm
2, generated output density then reaches 317mW/cm
2.
Embodiment 4
The Nafion solution being 0.5% by isopropyl alcohol and mass concentration mixes according to volume ratio 5:1, obtain the mixed solution of isopropyl alcohol and Nafion, embodiment 1 gained N-Fe-HPC catalyst 10mg is distributed in the mixed solution of above-mentioned 12ml isopropyl alcohol and Nafion, under ultrasonication, obtains homogeneous catalyst agent solution.Then be sprayed on the carbon paper of hydrophobic treatment that (carrying capacity is 2.0mg/cm
2), 60 DEG C of dryings prepare air electrode in 30 minutes, simultaneously using the zinc paper tinsel identical with carbon paper area as negative electrode, potassium hydroxide solution reaction cell groove air electrode, zinc paper tinsel being put into 6mol/L forms actual two electrode zinc-empty battery, utilized by zinc and air cell blue electric system to test, test condition is respectively 10mA/cm
2and 100mA/cm
2constant-current discharge, until zine plate runs out of.
Test result as shown in Figure 4, the low current density 10mA/cm of zinc and air cell
2with high current density 100mA/cm
2in discharge process, voltage does not all significantly decrease, particularly under low discharging current, discharge sustain 100 hours, voltage does not still significantly decrease, and illustrates that the discharge performance of battery is very stable, N-M-HPC catalyst has excellent stability, has fine practical potential.
Embodiment 5
The Nafion solution being 0.5% by isopropyl alcohol and mass concentration mixes according to volume ratio 3:1, obtain the mixed solution of isopropyl alcohol and Nafion, the embodiment 1 gained N-Fe-HPC catalyst of 10mg is scattered in the mixed solution of above-mentioned 12ml isopropyl alcohol and Nafion, under ultrasonication, obtains homogeneous catalyst agent solution.Then be sprayed on the carbon paper of hydrophobic treatment that (carrying capacity is 2.0mg/cm
2), 60 DEG C of dryings prepare air electrode in 30 minutes, simultaneously using the zinc paper tinsel identical with carbon paper area as negative electrode, potassium hydroxide solution reaction cell groove air electrode, zinc paper tinsel being put into 6mol/L forms actual two electrode zinc-empty battery, utilized by zinc and air cell blue electric system to test, test condition is respectively 10mA/cm
2constant-current discharge, changes alkali lye and zine plate reaching 45 hours, retests open circuit voltage and constant-current discharge voltage after Model For Transverse-discharge Flow Type.As can be seen from Fig. 5 result, change alkali lye and zine plate after carrying out electric discharge for a long time with the air electrode become prepared by N-Fe-HPC, open circuit voltage OCV and constant-current discharge voltage almost return to former level again.Illustrate that the small decline that battery performance occurs is because the consumption of alkali lye and zine plate causes, confirm the stability of this invention catalyst excellence further, the electric discharge of flow battery scale can be applied to.
Claims (12)
1. nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst, it is characterized in that, the raw material of described catalyst comprises: mass content be 10 ~ 60% template, mass content be 5 ~ 60% nitrogenous high polymer and mass content be the transition metal salt of 15 ~ 40%.
2. a kind of nitrogen according to claim 1/transition metal codope multi-stage porous carbon oxygen reduction catalyst, is characterized in that, described template is the colloid of the powder of silicon dioxide, the aqueous solution of silicon dioxide, the ethanolic solution of silicon dioxide or silicon dioxide; Wherein, the diameier of silicon dioxide is 5 ~ 1000nm.
3. a kind of nitrogen according to claim 1/transition metal codope multi-stage porous carbon oxygen reduction catalyst, it is characterized in that, described nitrogenous high polymer is polyquaternary amine [two (2-chloroethyl) ether-alt-1, two [3-(dimethylamino) propyl group] urea of 3-], the polymer of chlorination-1-vinyl-3-methyl isophthalic acid H-imidazoles and l-vinyl-2-pyrrolidone, at least one in poly-(diallyldimethylammonium chloride) and propenyl dimethyl ammonium chloride-acrylamide.
4. a kind of nitrogen according to claim 1/transition metal codope multi-stage porous carbon oxygen reduction catalyst, it is characterized in that, described transition metal salt is at least one in ferrous sulfate, cobaltous sulfate, nickelous sulfate and frerrous chloride.
5. a preparation method for nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst, comprising:
(1) nitrogenous high polymer, template and transition metal salt are dissolved in respectively in solvent, the nitrogenous high polymeric solution obtained, template solution and transition metal salting liquid mix under agitation, dry, obtain presoma; Wherein, presoma comprise mass content be 10 ~ 60% template, mass content be 5 ~ 60% nitrogenous high polymer and mass content be the transition metal salt of 15 ~ 40%, mass content with the gross mass of presoma for benchmark;
(2) presoma in step (1) is warming up to 700 ~ 1000 DEG C of roasting 2 ~ 4h under inert gas atmosphere protection, obtains catalyst intermediate;
(3) by catalyst intermediate alkali cleaning process 48 ~ 72h in step (2), cleaning, dry, obtain a nitrogen/transition metal codope multi-stage porous carbon material;
(4) by nitrogen/transition metal codope multi-stage porous carbon material 60 ~ 85 DEG C of pickling processes 10 ~ 24h in step (3); suction filtration, cleaning; dry; and 700 ~ 1000 DEG C of roasting 1 ~ 2h are warming up under inert gas atmosphere protection, obtain nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst.
6. the preparation method of a kind of nitrogen according to claim 5/transition metal codope multi-stage porous carbon oxygen reduction catalyst, it is characterized in that, in described step (1), the mass fraction of nitrogenous high polymeric solution is 5% ~ 60%; The mass fraction of template solution is 10% ~ 60%; The mass fraction of transition metal salting liquid is 15% ~ 40%.
7. the preparation method of a kind of nitrogen according to claim 5/transition metal codope multi-stage porous carbon oxygen reduction catalyst, is characterized in that, in described step (1), solvent is hydrochloric acid; Dry temperature is 50 ~ 90 DEG C.
8. the preparation method of a kind of nitrogen according to claim 5/transition metal codope multi-stage porous carbon oxygen reduction catalyst, is characterized in that, alkali cleaning is treated to the alkali cleaning at room temperature ~ 60 DEG C of excessive sodium hydroxide solution in described step (3).
9. the preparation method of a kind of nitrogen according to claim 5/transition metal codope multi-stage porous carbon oxygen reduction catalyst, is characterized in that, in described step (4), pickling processes is excessive sulfuric acid treatment.
10. an application for nitrogen as claimed in claim 1/transition metal codope multi-stage porous carbon oxygen reduction catalyst, is characterized in that, described nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst is applied to the air electrode preparing metal-air cell.
The application of 11. a kind of nitrogen according to claim 10/transition metal codope multi-stage porous carbon oxygen reduction catalyst, is characterized in that, described metal-air cell is zinc-empty battery, aluminium-empty battery or magnesium-empty battery.
The application of 12. a kind of nitrogen according to claim 10/transition metal codope multi-stage porous carbon oxygen reduction catalyst, it is characterized in that, the preparation method of described air electrode comprises: isopropyl alcohol and Nafion solution are obtained mixed solution according to volume ratio 5:1 ~ 3:1, by nitrogen/transition metal codope multi-stage porous carbon oxygen reduction catalyst is distributed in mixed solution, ultrasonic, be sprayed in gas-diffusion electrode, dry, obtain air electrode.
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