CN110504456A - It is a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and its preparation method and application - Google Patents
It is a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and its preparation method and application Download PDFInfo
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- CN110504456A CN110504456A CN201910645654.2A CN201910645654A CN110504456A CN 110504456 A CN110504456 A CN 110504456A CN 201910645654 A CN201910645654 A CN 201910645654A CN 110504456 A CN110504456 A CN 110504456A
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- H01M4/8605—Porous electrodes
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention relates to a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and its preparation method and application; described method includes following steps: using hexabromobenzene and pyridine as raw material; the crude product of nitrogen oxygen doping ball/piece porous carbon materials is made using solvent-thermal method direct step original position dehalogenation polymerization reaction and is carbonized under inert gas protection using temperature programming, is ground after cooling and obtains nitrogen oxygen doping ball/piece porous carbon materials.The nitrogen oxygen doping ball/piece porous carbon materials its stable structure, (material resistance is only 15.96m Ω, conductivity 8.11*10 to good conductivity‑4Ω m), active site it is more, can be used to the oxygen reduction electrode for preparing fuel cell, so as in fuel cell, and show good chemical property；The inexpensive large scale preparation of nitrogen oxygen doping ball/piece porous carbon materials may be implemented in simple, the environmental-friendly and excellent chemical property in view of this method synthesis technology, therefore has a good application prospect and industrialization potential.
Description
Technical field
The present invention relates to a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and preparation method thereof and answers
With belonging to inorganic functional material field.
Background technique
As the increasingly depleted and environmental degradation problem of fossil energy is got worse, development efficiently, the cleaning energy of safety
Source and technology are very urgent.Reproducible energy technology is cleaned, if fuel cell is to be expected to solve the current energy and environment
The important technology of challenge.Wherein elctro-catalyst is the core of above-mentioned renewable energy technologies.Currently, based on its excellent hydrogen reduction
Catalytic capability and high current density, putative best oxygen reduction electro-catalyst are still platinum-base catalyst.But due to
Platinum-sill is at high price and methanol tolerance and CO tolerance catalysts are indifferent limits it in the large-scale application of business.
In order to solve the problems, such as that above-mentioned elctro-catalyst exists, non-metallic catalyst is living due to its similar excellent hydrogen reduction
Property, the ability of higher methanol tolerance and CO tolerance catalysts, have been subjected to researcher and have widely paid close attention to.Wherein, Heteroatom doping
Nanostructured carbon material (such as carbon nanotube, graphene, porous carbon, carbon quantum dot), have various structures, it is resourceful, lead
Electrically the advantages that good, large specific surface area, strong, environmental-friendly, surface nature is unique resistance to corrosion, it is considered most promising to be
Substitute noble metal catalyst.
If CN105186010B provides a kind of preparation method of hierarchical porous structure nitrogen-doped carbon oxygen reduction catalyst, belong to combustion
Expect battery technology field.The invention uses Eutectic molten salt of the freeze-drying method preparation with 3 D stereo macroporous structure first,
Then using Eutectic molten salt as template, nitrogenous precursor is adulterated, ammonium persulfate is oxidant, and molysite is co-catalyst, using oxidation
Polymerization causes nitrogenous precursor oxidation polymerization on Eutectic molten salt surface, finally carries out high temperature pyrolysis and removes Eutectic molten salt.It should
The hierarchical porous structure nitrogen-doped carbon oxygen reduction catalyst of invention preparation can effectively avoid polymer with nitrogen presoma in pyrocarbon
Pyrolysis loss, structure collapses and sintering during change improve catalyst production and N doping efficiency, and can produce a large amount of
Micropore, mesoporous and macropore improve the mass-transfer efficiency of oxygen and water.But this method is complicated for operation, doping is low, low output, therefore
Large-scale popularization and application are not can be carried out.
CN105609793A more particularly to a kind of dual site catalytic oxidation-reduction iron nitrogen-doped graphene porous material and
Preparation method and application.This porous material is by the carbon-coated cementite insertion N doping porous graphene band network of graphite
It is formed in structure.By preparation graphene oxide solution and suitable conducting polymer pyrroles is added wherein, then hydro-thermal obtains
To uniform hydrogel, hydrogel is subjected to oxidation polymerization with ferric iron, is then dispersed in fresh trivalent ferrous solution and completes
Absorption is heat-treated after through dry and high temperature carbonization, finally with diluted acid remove iron phase nonactive, free in reaction system to
Obtain the graphene porous material of final iron N doping.But the iron nitrogen-doped graphene porous material preparation of this method preparation
Method is cumbersome, and will affect the cyclical stability of material into metallic atom, therefore may not apply to industrialized production.
The patent of CN105186010A discloses one kind and prepares solid polymer by template of Eutectic molten salt, then high temperature solution
The method that hot preparation goes out nitrogen-doped carbon oxygen reduction catalyst, although the hierarchical porous structure nitrogen-doped carbon material pore structure prepared is rich
Richness, but the raw material that the method uses is various, higher cost, complex process.
The patent of CN107282081A is disclosed one kind and is mentioned with carbon source, nitrogen source, zinc chloride and five hydrated basic magnesium carbonates etc.
For hetero atom and as the method for reducing agent synthesis bulk multi-hole nitrogen-doped carbon oxygen reduction catalyst, although this method use scope
Extensively, but technical process is relative complex and the performance of oxygen-reducing catalyst that is prepared is general, is not able to satisfy production and living to oxygen
The requirement of reducing catalyst.
Single Heteroatom doping carbon material and multiple Heteroatom doping become the research emphasis of vast researcher, but close
It is still the difficult point of scientific research at the carbon material for accurately regulating and controlling multiple Heteroatom doping amount and type.It introduces and mixes in carbon material
When hetero atom, traditional method either reaches doping effect the mode still post-processed by way of physical blending, this
Two ways doping efficiency is low, and doping is uneven and can only carry out edge doping, and makes the performance of carbon material unstable, into
And influence its performance.Based on this, it is necessary to this further improvement.
Summary of the invention
The technical problem to be solved by the embodiment of the invention is that providing a kind of based on nitrogen oxygen doping ball/piece porous carbon
Oxygen reduction electrode of material and its preparation method and application.
As the first aspect of the invention, technical solution be the following steps are included:
(1) nitrogen oxygen doping multistage pore canal carbon material is prepared, comprising the following steps:
S1: hexabromobenzene and pyridine are subjected to confined reaction at high temperature under high pressure；The confined reaction is that dehalogenation polymerization in situ is anti-
It answers.
S2: after reaction, pressure release to normal pressure, and cooled to room temperature, it is supreme with deionized water and petroleum ether
Layer liquid is transparent, and obtained solid after washing is dry, obtains drying sample；
S3: carrying out high-temperature roasting processing for the drying sample under inert gas protection, mixes to obtain the nitrogen oxygen
Miscellaneous multistage pore canal carbon material；
(2) method of oxygen reduction electrode preparation, described method includes following steps:
A, be polishing in 0.05-1.0 μm of aluminium oxide water slurry, polishing in granularity by glass-carbon electrode, then successively acetone,
It supersound washing 20-40 seconds in dehydrated alcohol and high purity water, is dried with nitrogen, obtains pretreatment glass-carbon electrode；
B, the nitrogen oxygen doping ball/piece porous carbon materials and Nafion solution are dispersed in the mixed solution of ethanol water
In, then ultrasonic disperse 5-15 minutes, obtain mixed solution；The mixed solution is dripped into the pre- place several times
It manages on glass-carbon electrode, drying at room temperature is to get oxygen reduction electrode.
Wherein, the acetone, anhydrous in the step (A) in the preparation method of oxygen reduction electrode of the present invention
There is no particular limitation for the dosage of ethyl alcohol, high purity water and Nafion, this be technical staff in electrode preparation field can properly into
What row was determined and was selected, it is no longer described in detail herein；The acetone, dehydrated alcohol and Nafion, three are preparation neck
The common known raw material in domain, can be commercially-available by multiple channel, and this is no longer going to repeat them.
In the preparation method of the nitrogen oxygen doping ball/piece porous carbon materials of the invention, in step sl, the reaction
Pressure is 2-8MPa, may be, for example, 2MPa, 4MPa, 6MPa or 8MPa.
In the preparation method of the nitrogen oxygen doping ball/piece porous carbon materials of the invention, in step sl, the reaction time
It is 2-10 hours, may be, for example, 2 hours, 4 hours, 6 hours, 8 hours or 10 hours.
In the preparation method of the nitrogen oxygen doping ball/piece porous carbon materials of the invention, in step sl, the hexabromo
The molar ratio of benzene and pyridine is 0.01~0.03, may be, for example, 1:100,1:90,1:80,1:70,1:60 or 1:50.
In the preparation method of the nitrogen oxygen doping ball/piece porous carbon materials of the invention, in step sl, reaction temperature
It is 140-260 DEG C, may be, for example, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C or 260 DEG C, preferably 180-220
DEG C, optimum temperature is 200 DEG C.
In the preparation method of the nitrogen oxygen doping ball/piece porous carbon materials of the invention, in step s 2, obtained solid
Petroleum ether can be spent, washing times can be 2-4 times.
In the preparation method of the nitrogen oxygen doping ball/piece porous carbon materials of the invention, in step s 2, vacuum drying
Temperature is 60-100 DEG C, may be, for example, 60 DEG C, 80 DEG C or 100 DEG C；Drying time is 8-12 hours, may be, for example, 8 hours, it is 10 small
When or 12 hours.
In the preparation method of the nitrogen oxygen doping ball/piece porous carbon materials of the invention, in step s3, the high temperature
The temperature of processing is 800-1100 DEG C, may be, for example, 800 DEG C, 900 DEG C, 1000 DEG C and 1100 DEG C, preferably 900-1100 DEG C, most
Good heat treatment temperature is 1000 DEG C.
In the preparation method of the nitrogen oxygen doping ball/piece porous carbon materials of the invention, in step s3, the high temperature
Handling the time is 1-3 hours, be may be, for example, 1 hour, 2 hours or 3 hours.
In the preparation method of the nitrogen oxygen doping ball/piece porous carbon materials of the invention, in step s3, the inertia
Gas is nitrogen or argon gas.
In conclusion the high-temperature roasting in the step 3 is handled, i.e., by the drying sample in this temperature range with it is lazy
Property gas is divided into middle placement 1-3 hours, to obtain the nitrogen oxygen doping ball/piece porous carbon materials of the invention.
The inventors discovered that can obtain having the nitrogen oxygen of superior electrical performance to mix when using preparation method so
Miscellaneous ball/piece porous carbon materials, and when changing certain technological parameters, performance is caused to have significant decrease.
Nitrogen oxygen doping multistage pore canal carbon material prepared by step (1) of the present invention has excellent electric property, material electricity
It hinders relatively small, so as to be applied to lithium cell cathode material field, has a good application prospect and industrialization potential.The nitrogen
Oxygen doping multistage pore canal carbon material can also be in the purposes in assembling lithium battery.
Inventors discovered through research that the negative electrode material comprising the nitrogen oxygen doping ball/piece porous carbon materials has well
Chemical property, such as have hydrogen reduction spike potential (- 0.118V Vs.Ag/AgCl), the half wave potential (- 0.1V of corrigendum
Vs.Ag/AgCl), the superior performance such as have extended cycle life, be low in cost, is environmental-friendly, so as to be applied to fuel cell electrode
Material Field.
Based on the studies above as a result, proposing the purpose of the second aspect of the invention, one kind is provided and is obtained based on the above method
The oxygen reduction electrode arrived.
As described above, the oxygen reduction electrode is due to a variety of excellent chemical properties, so as to apply it to
In fuel cell, and then obtain the fuel cell with excellent properties.
As described above, the present invention provides a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and its
Preparation method, purposes and the oxygen reduction electrode comprising it, the nitrogen oxygen doping ball/piece porous carbon materials have excellent performance,
It can be used to prepare the oxygen reduction electrode of fuel cell, so as to be used in fuel cell, and show good electrochemistry
Can, there is huge application potential and industrial value in electrochemical field.
Nitrogen oxygen doping ball/piece porous carbon materials of the invention, the carbon ball of this Heteroatom doping and carbon nanosheet it is porous
Road composite construction increases the active site of material, improves the stability of material.This material preparation cost is cheap, synthesis
Method has excellent hydrogen reduction (ORR) performance as fuel cell electrode material, therefore, before having good industrialized production
Scape.
Nitrogen oxygen doping ball/piece porous carbon materials are made using solvent-thermal method direct step original position dehalogenation polymerization reaction in the present invention
Crude product and be carbonized under inert gas protection using temperature programming, it is cooling after grinding obtain nitrogen oxygen doping ball/piece porous carbon
Material.The nitrogen oxygen doping ball/piece porous carbon materials its stable structure, (material resistance is only 15.96m Ω, conductance to good conductivity
Rate is 8.11*10-4Ω m), active site is more, can be used to the oxygen reduction electrode for preparing fuel cell, so as to for firing
Expect in battery, and shows good chemical property；Simple, the environmental-friendly and excellent electricity in view of this method synthesis technology
Chemical property may be implemented the inexpensive large scale preparation of nitrogen oxygen doping ball/piece porous carbon materials, therefore have good application
Prospect and industrialization potential.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without any creative labor, according to
These attached drawings obtain other attached drawings and still fall within scope of the invention.
Four small figures in Fig. 1 be followed successively by from left to right, from top to bottom nitrogen oxygen doping ball obtained by the embodiment of the present invention 1/
The scanning electron microscope (SEM) photograph (SEM) of piece porous carbon materials, for spherical and flaky material transmission electron microscope picture (TEM) and high-resolution
(HRTEM) figure and distribution diagram of element (EDS).
Fig. 2 is nitrogen oxygen doping ball/piece porous carbon materials Raman figure of the embodiment of the present invention 1；
Fig. 3 is nitrogen oxygen doping ball/piece porous carbon materials nitrogen adsorption curve graph of the embodiment of the present invention 1；
Fig. 4 is nitrogen oxygen doping ball/piece porous carbon materials graph of pore diameter distribution of the embodiment of the present invention 1；
Fig. 5 is nitrogen oxygen doping ball/piece porous carbon materials XPS high-resolution C1s spectrogram of the embodiment of the present invention 1；
Fig. 6 is nitrogen oxygen doping ball/piece porous carbon materials XPS high-resolution N1s spectrogram using the embodiment of the present invention 1；
Fig. 7 is nitrogen oxygen doping ball/piece porous carbon materials XPS high-resolution O1s spectrogram using the embodiment of the present invention 1；
Fig. 8 is oxygen reduction electrode prepared by nitrogen oxygen doping ball/piece porous carbon materials using the embodiment of the present invention 1 to oxygen
Gas restores the CV curve under argon gas/oxygen saturation state, and sweeping speed is 10mV/s；
Fig. 9 is oxygen reduction electrode prepared by nitrogen oxygen doping ball/piece porous carbon materials using the embodiment of the present invention 1 in oxygen
Under gas saturation state, under different rotating speeds to the linear scan curve graph of oxygen reduction, sweeping speed is 10mV/s；
Figure 10 is oxygen reduction electrode prepared by nitrogen oxygen doping ball/piece porous carbon materials using the embodiment of the present invention 1
Koutecky-Levich figure；
Figure 11 be oxygen reduction electrode prepared by nitrogen oxygen doping ball/piece porous carbon materials using the embodiment of the present invention 1 with
The anti methanol toxication test comparison chart of 20%Pt/C catalyst；
Figure 12 is oxygen reduction electrode prepared by nitrogen oxygen doping ball/piece porous carbon materials using the embodiment of the present invention 1
Stability test figure；
Figure 13 is nitrogen oxygen doping ball/piece porous carbon materials using Example 1 and Example 2 of the present invention -3 and oxygen is made also
Primary electrode CV curve under oxygen saturation state to oxygen reduction, sweeping speed is 10mV/s；
Figure 14 is nitrogen oxygen doping ball/piece porous carbon materials using the embodiment of the present invention 1 and embodiment 4-5 and oxygen is made also
Primary electrode CV curve under oxygen saturation state to oxygen reduction, sweeping speed is 10mV/s.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
1. nitrogen oxygen doping ball/piece porous carbon materials preparation method
Embodiment 1
S1: hexabromobenzene and pyridine are carried out confined reaction 6 hours at the reaction pressure of 3MPa and 200 DEG C；Wherein, described
The mass ratio of hexabromobenzene and pyridine is 1:80；
S2: after reaction, pressure release to normal pressure, and cooled to room temperature, obtained solid petroleum ether is sufficiently washed 3
It is secondary, be dried in vacuo 10 hours at 40 DEG C, obtain drying sample；
S3: under nitrogen protection by the drying sample, high-temperature process 2 hours at 1000 DEG C, to obtain the nitrogen
Oxygen doping ball/piece porous carbon materials, is named as P1.
Embodiment 2-3: the investigation of reaction ratio in step S1
In addition to the quality of the reaction hexabromobenzene in step S1 is replaced with 2g and 6g respectively, other operations are constant, thus
It is sequentially carried out a 2-3, gained nitrogen oxygen doping ball/piece porous carbon materials are successively named as P2 and P3.
Embodiment 4-6: the investigation of step S3 high temperature treatment temperature
In addition to the high-temperature process temperature in step S3 is replaced with 900 DEG C and 1100 DEG C respectively, other operations are constant, from
And it is sequentially carried out a 4-5, gained nitrogen oxygen doping ball/piece porous carbon materials are successively named as P4 and P5.
2. prepared by nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode
Embodiment 7: the preparation method of oxygen reduction electrode includes the following steps
(A) first polishing, polishing in the aluminium oxide water slurry that granularity is 1.0 μm by glass-carbon electrode, then successively in acetone, nothing
It supersound washing 20-40 seconds in water-ethanol and high purity water, is dried with nitrogen, above-mentioned step is then repeated in 0.05 μm of aluminium oxide water slurry
Suddenly, pretreatment glass-carbon electrode is finally obtained；
(B) a certain amount of above-mentioned nitrogen oxygen doping ball/piece porous carbon materials are weighed and Nafion solution is dispersed in ethanol water
In mixed solution, then ultrasonic disperse 5-15 minutes, mixed solution is obtained；The mixed solution is dripped to several times
On the pretreatment glass-carbon electrode, drying at room temperature is to get oxygen reduction electrode of the invention.Wherein ionized water 0.8mL, dehydrated alcohol
20 μ L of 0.2mL, Nafion, nitrogen oxygen doping ball/piece porous carbon materials quality are 4.00mg.
3. the test of nitrogen oxygen doping ball/piece porous carbon materials electrode
Using nitrogen oxygen doping ball/piece porous carbon materials electrode as working electrode, Ag/AgCl is reference electrode, and platinized platinum is to electricity
Nitrogen oxygen doping ball/piece is tested in 0~-1.0V of potential window at 25 DEG C with Autolab in 0.1M KOH electrolyte solution in pole
The hydrogen reduction performance of porous carbon materials electrode.Test result shows nitrogen oxygen doping ball/piece porous carbon materials electrode, hydrogen reduction peak
Current potential is -0.118V (Vs.Ag/AgCl), half wave potential is -0.1V (Vs.Ag/AgCl).With nitrogen oxygen doping ball/piece porous carbon
Expect that the relative current densities of electrode are rear for 24 hours without obvious decaying in continuance test, last retention still intimate 100% or so is said
Bright composite material P1 has brilliant cyclical stability.
Microscopic sdIBM-2+2q.p.approach
The nitrogen oxygen doping ball/piece porous carbon materials P1 resulting to embodiment 1 has carried out the microcosmic of multiple and different means
Characterization is as a result as follows:
1, four small figures in Fig. 1 are followed successively by nitrogen oxygen doping obtained by the embodiment of the present invention 1 from left to right, from top to bottom
Ball/piece porous carbon materials scanning electron microscope (SEM) photograph (SEM), for spherical and flaky material transmission electron microscope picture (TEM) and high-resolution
(HRTEM) figure and distribution diagram of element (EDS).
It, can seeing with deep layer from TEM figure from SEM figure it can be seen that sheet and spherical composite material is presented in the material
Material is made of the graphene film of fold and forms with microballoon；From HRTEM it can also be seen that material has pore structure abundant.From
It can be seen that there is only nitrogen, carbon and oxygen elements for material in EDS, and be uniformly distributed in the material.
2, the I of material is calculated from the Raman figure of Fig. 2D/IG=0.92, illustrate that degree of graphitization is higher in P1, is graphitized
Degree height illustrates conducting electricity very well for material；But it also suffers from certain drawbacks simultaneously, defect provides more work for electro-catalysis
Property site.
3, it can be seen that the adsorption curve belongs to typical II adsorption curve and possesses H3 from the nitrogen adsorption curve of Fig. 3
Type hysteresis loop, is mutually authenticated with Fig. 4.
4, there are micropores, mesoporous and macropore composition by available P1 from the graph of pore diameter distribution of Fig. 4.It is mesoporous and micropore to deposit
Increasing the active site quantity of catalysis reaction.
5, from the XPS high-resolution C1s spectrogram of Fig. 5 it is found that bond energy 284.8eV be C=C/C-C key, 285.6eV C-N
Key, 286.3eV are C=O key, 290.0eV COOR；Wherein the content of carbon accounts for 94.39%.
6, from the XPS high-resolution N1s spectrogram of Fig. 6 it is found that bond energy 401.2eV be pyridine nitrogen key, 402.5eV be quaternary amine nitrogen
Key, 406.7eV are pyridine oxide nitrogen key, 406.7eV N-OxFunctional group；Hetero atom nitrogen is 3.73%, these functional groups deposit
More active sites are being provided for reaction.
7, from the XPS high-resolution O1s spectrogram of Fig. 7 it is found that bond energy 532.2eV be C=O key, 533.2eV be C-O key,
534.0eV is COOR, and the content of hetero atom oxygen atom is 1.75%；
Electrochemical property test
1, Fig. 8 is CV curve of the P1 electrode to oxygen reduction under argon gas/oxygen saturation state, and sweeping speed is 10mV/s.Its
In, the CV curve of top-down two closed circles difference argon gas saturation state and oxygen saturation state.It can be seen by the figure
Out, under argon gas saturation state, there is not reduction peak, only shows capacitance behavior in the CV curve approximation rectangle of P1 electrode.But
Under oxygen saturation state, there is apparent reduction peak, reduction spike potential is -0.118V, shows composite material P1 to oxygen
There is good response.
2, Fig. 9 be P1 electrode under oxygen saturation state, under different rotating speeds to the linear scan curve graph of oxygen reduction,
Sweeping speed is 10mV/s.Wherein, in Far Left, top-down revolving speed is respectively 400,625,900,1225,1600,2025 and
2500rpm。
It can be seen from the figure that between voltage range -0.17~0V, with the increase of revolving speed, hydrogen reduction electric current density
It does not change significantly, shows in this voltage range, hydrogen reduction electric current is mainly by dynamics Controlling.And in voltage range -1
Between~-0.17V, with the increase of revolving speed, hydrogen reduction electric current density constantly increases, and illustrates in this voltage range, mainly
It is controlled by diffusion.
3, Figure 10 is that P1 electrode according to LSV curve is combined Koutecky-Levich formula, and it is basic that material is calculated
For 4 electronics transfers.
4, Figure 11 is the anti methanol toxication test comparison chart of P1 electrode Yu 20%Pt/C catalyst.Wherein, in Far Left, certainly
Upper and lower respectively P1 electrode and 20%Pt/C.It can be seen from the figure that the methanol aqueous solution of 3mol/L, P1 are added in 300s
The current density of electrode is held essentially constant, and the current density change of 20%Pt/C is clearly.This illustrates composite material
P1 has better anti methanol toxication compared with commercialized 20%Pt/C.
5, Figure 12 is the stability test figure of P1 electrode.The cyclical stability is steady by the circulation of chronoamperometry test
It is qualitative, test condition are as follows: in O2It is tested in the KOH aqueous solution of the 0.1mol/L of saturation, revolving speed 1600rpm ,-
It is tested for 24 hours under 0.25V current potential.It can be seen from the figure that the relative current densities of P1 electrode are in continuance test, rear nothing obviously declines for 24 hours
Subtract, last retention still intimate 100% or so, illustrates that composite material P1 has brilliant cyclical stability.
The electric property of other materials characterizes
1, Figure 13 is nitrogen oxygen doping ball/piece porous carbon materials using Example 1 and Example 2 of the present invention -3 and oxygen is made
CV curve of the reducing electrode to oxygen reduction under oxygen saturation state, sweeping speed is 10mV/s.It can be seen from the figure that P1 electrode
It is compared with P2 electrode, P3 electrode, spike potential and take-off potential calibration, illustrates that composite material P1 has excellent hydrogen reduction
Energy.
Figure 14 is nitrogen oxygen doping ball/piece porous carbon materials using the embodiment of the present invention 1 and embodiment 4-5 and oxygen is made also
CV curve of the primary electrode to oxygen reduction under oxygen saturation state, sweeping speed is 10mV/s.It can be seen from the figure that P1 electrode and
P4 electrode, P5 electrode are compared, spike potential and take-off potential calibration, illustrate that composite material P1 has excellent hydrogen reduction performance.
As described above, the present invention provides a kind of nitrogen oxygen doping ball/piece porous carbon materials preparation method and uses, and
Oxygen reduction electrode as made from it, the material have excellent a variety of chemical properties, can be used to prepare oxygen reduction electrode, from
And can be applied in fuel cell, excellent chemical property is shown, is had a good application prospect in electrochemical field
And industrialization potential.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.
Claims (9)
1. a kind of preparation method based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode, it is characterised in that including with
Lower step:
(1) nitrogen oxygen doping multistage pore canal carbon material is prepared, comprising the following steps:
S1: hexabromobenzene and pyridine are subjected to confined reaction at high temperature under high pressure；
S2: after reaction, pressure release to normal pressure, and cooled to room temperature, with deionized water and petroleum ether to upper liquid
It is transparent, obtained solid after washing is dry, obtain drying sample；
S3: carrying out high-temperature roasting processing for the drying sample under inert gas protection, so that it is more to obtain the nitrogen oxygen doping
Grade duct carbon material；
(2) method of oxygen reduction electrode preparation, described method includes following steps:
It A, is polishing in 0.05-1.0 μm of aluminium oxide water slurry, polishing in granularity by glass-carbon electrode, then successively in acetone, anhydrous
It supersound washing 20-40 seconds in ethyl alcohol and high purity water, is dried with nitrogen, obtains pretreatment glass-carbon electrode；
B, the nitrogen oxygen doping multistage pore canal carbon material and Nafion solution are dispersed in the mixed solution of ethanol water, then
Ultrasonic disperse 5-15 minutes, obtain mixed solution；The mixed solution is dripped into the pretreatment glass carbon several times
On electrode, drying at room temperature is to get oxygen reduction electrode.
2. a kind of preparation side based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode according to claim 1
Method, it is characterised in that: hexabromobenzene and the molar ratio of pyridine are 0.01~0.03.
3. a kind of preparation side based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode according to claim 1
Method, it is characterised in that: in step sl, the reaction pressure is 2-8 MPa, and the reaction time is 2-10 hours.
4. a kind of preparation side based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode according to claim 1
Method, it is characterised in that: in step sl, reaction temperature is 140-260 DEG C.
5. a kind of preparation side based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode according to claim 1
Method, it is characterised in that: in step s 2, drying temperature is 60-100 DEG C, and drying time is 8-12 hours.
6. a kind of preparation side based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode according to claim 1
Method, it is characterised in that: in step s3, the temperature of the high-temperature process is 800-1100 DEG C.
7. a kind of preparation side based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode according to claim 1
Method, it is characterised in that: in step s3, the high-temperature process time is 1-3 hours.
8. a kind of obtained oxygen reduction electrode of preparation method as described in one of claim 1-7.
9. a kind of fuel cell including oxygen reduction electrode according to any one of claims 8.
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