CN106602092A - Preparation method for single-walled carbon nanotube (SWCNT) hollow ball oxygen reduction catalyst, and application of SWCNT hollow ball oxygen reduction catalyst - Google Patents
Preparation method for single-walled carbon nanotube (SWCNT) hollow ball oxygen reduction catalyst, and application of SWCNT hollow ball oxygen reduction catalyst Download PDFInfo
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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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- 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 invention belongs to the field of energy, and particularly relates to a preparation method for a single-walled carbon nanotube (SWCNT) hollow ball oxygen reduction catalyst, and an application of the SWCNT hollow ball oxygen reduction catalyst. The SWCNT hollow ball oxygen reduction catalyst is an SWCNT hollow ball oxygen reduction catalyst with co-doping of a transition metal and nitrogen, and the preparation method comprises the following steps: monodispersed oxidized SWCNTs are firstly self-assembled into SWCNT balls in the shape of hollow balls through the hard template method; the SWCNT hollow balls and a transition metal N4 cyclic compound are then sufficiently mixed; and calcination is then carried out in an ammonia or inert atmosphere to achieve the co-doping of the transition metal and the nitrogen, so that the SWCNT hollow ball oxygen reduction catalyst is obtained. The catalyst achieves efficient oxygen reduction catalysis performance, and can be used as an air electrode catalyst for hydrogen-oxygen fuel cells, zinc-air fuel cells, magnesium-air fuel cells, and aluminum-air fuel cells.
Description
Technical field
The invention belongs to energy field, more particularly to a kind of preparation side of SWCN hollow ball oxygen reduction catalyst
Method and application.
Background technology
Energy shortage and environmental pollution are two hang-ups that today's society faces.Fuel cell is straight by chemical energy as one kind
Switch through the TRT for turning to electric energy, have the advantages that energy density is big, high conversion efficiency, cleanliness without any pollution, it is considered to be
A kind of green clean energy resource of sustainable development.Therefore, developing fuel cell becomes the important way for solving the problems, such as energy and environment
One of footpath.In a fuel cell, including hydrogen-oxygen fuel cell and metal air fuel cell, cathodic oxygen reduction catalyst is to affect
The key factor of battery performance.At present, the cathod catalyst that fuel cell is used is mainly Pt base catalyst, because platinum base catalysis
Agent has higher oxygen reduction catalystses activity.However, platinum based catalyst remains two problems：One is expensive, money
Source is rare；Two is easily to be poisoned by organic-fuel and catalyst is easily reunited and grows up and reduce catalyst life.Therefore, develop
Go out the non noble metal oxygen reduction catalyst of high activity, high stability substituting the commodity of the platinum based catalyst to fuel cell of costliness
Change development and application significant.
Material with carbon element is abundant, with low cost due to material source, and with satisfactory electrical conductivity, mechanical performance and chemically stable
Property, it is also easy to be modified doping, it is widely used for fuel-cell catalyst carrier by people.In recent years, with various New Type of Carbon
The appearance and exploitation of nano material (such as Graphene, CNT, carbon nanohorn and ordered mesopore carbon), and for as oxygen
The doping carrier of reducing catalyst so that the research and development of oxygen reduction catalyst have obtained very big progress.Particularly transition is golden
The nano-carbon material of category and nitrogen codope, because its material source is abundant, with low cost, oxygen reduction catalytic activity is high, is recognized
To be one of most potential non-precious metal catalyst in fuel cells applications.Result of study shows, these new nanometers
C catalyst typically exhibits even more superior electrocatalysis characteristic suitable with business platinum carbon.However, due to these nano carbon materials
Material (such as CNT, Graphene) would generally be stacked with and assemble, and cause many active sites to be blanked so as to urge
Agent is difficult to give full play of its due catalytic performance in actual battery applications.Particularly at higher current densities, its
Battery performance can show drastically to decline.So, solving an effective way of this problem is exactly carried out these nano-sized carbons
Orderly reconstruct, obtains the carbon nanomaterial assembly with big surface area and specific pore passage structure, not only can guarantee that and urges
Change the abundant exposure of avtive spot, effective passage of rapid mass transfer diffusion can be provided again, so as to further improve battery performance.
The content of the invention
For the problem that prior art is present, the invention provides a kind of SWCN hollow ball oxygen reduction catalyst
Preparation method and application.
A kind of preparation method of SWCN hollow ball oxygen reduction catalyst, the SWCN hollow ball oxygen
Reducing catalyst is transition metal and nitrogen co-doped SWCN hollow ball oxygen reduction catalyst, first will with hard template method
Monodispersed oxidation SWCN is self-assembled into the SWCN ball of hollow ball-shape, then SWCN is hollow
Ball is sufficiently mixed with transition metal N4 cycle compounds, and then transition metal and nitrogen are realized in calcining under ammonia or inert atmosphere
Codope, obtains SWCN hollow ball oxygen reduction catalyst.The catalyst has efficient hydrogen reduction catalytic performance,
Can be applicable to the air electricity of hydrogen-oxygen fuel cell, zinc/air fuel cell, magnesium air fuel cell and aluminium air-fuel battery
Electrode catalyst.
A kind of preparation method of SWCN hollow ball oxygen reduction catalyst, comprises the following steps：
1) single dispersing aoxidizes the preparation of SWCN：
By initial SWCN solid and potassium permanganate solid with 1：The proportioning of (1～4) is together added to excess
Concentrated sulfuric acid solution in, the reaction mixture for obtaining be placed in 40-70 DEG C of water-bath continue stirring reaction 1-6h, by what is reacted
After the dilution of mixed liquor deionized water, excessive hydrogen peroxide solution stirring more than 10min is added, through filtering with microporous membrane and dilute
After the washing of hydrochloric acid solution, the solid for obtaining again deionized water by high speed centrifugation wash to supernatant liquor be neutrality (PH=
6-7), then remove layer solid plus after deionized water is sufficiently stirred for, further after centrifugation, take homogeneous, the stable solution in upper strata, i.e.,
Obtain the monodispersed oxidation SWCN aqueous solution.
2) preparation of the SWCN assembly of hollow ball-shape：
First pass through ultrasound to be dispersed in water silicon dioxide microsphere template, add poly- (diallyl dimethyl ammonium chlorination
Ammonium) (PDDA) silicon dioxide microsphere template to be modified with PSS (PSS) aqueous solution so as to formation is carried
Positive charge PDDA/PSS composite modified silica ball template aqueous dispersion, then by above-mentioned modified silica spheres mould
Plate aqueous dispersion is added drop-wise in the monodispersed oxidation SWCN aqueous solution, and persistently stirs more than 0.5h, Jing Guojing
Sedimentation is put, its supernatant liquor is removed, the solid for obtaining is after 80 DEG C of oven dryings, then 500 DEG C of -1000 DEG C of annealing under an inert atmosphere
1-10h, finally at room temperature with 10%HF by silica etching removing, then after filtration washing and drying, obtains hollow ball
The SWCN assembly of shape.
3) preparation of transition metal and nitrogen co-doped SWCN hollow ball oxygen reduction catalyst：
By the SWCN assembly of transition metal N4 cycle compounds and hollow ball-shape with 1：The ratio of (0.5～4)
Uniform mixing, by mixture 1～6h is placed under 700 DEG C -1000 DEG C of inert atmosphere or anneals under ammonia atmosphere, obtains transition gold
Category and nitrogen co-doped SWCN hollow ball, that is, obtain SWCN hollow ball oxygen reduction catalyst.
A kind of application of SWCN hollow ball oxygen reduction catalyst of the present invention, the SWCN is hollow
Ball oxygen reduction catalyst is applied to hydrogen-oxygen fuel cell, zinc/air fuel cell, magnesium air fuel cell or aluminium air fuel
The air electrode catalyst of battery.
The preparation method of the air electrode is as follows：
By isopropanol and 5%Nafion solution according to volume ratio (10～20)：1 obtains mixed solution, by carbon-based complex group
Dress body oxygen reduction catalyst ultrasonic disperse is sprayed on carbon paper or carbon cloth electrode in mixed solution, is dried, and obtains air electricity
Pole, the carrying capacity of catalyst is 1mg/cm2。
Beneficial effects of the present invention are：
1) monodispersed SWCN Controllable assembly is adopted first into the SWCN of orderly hollow ball-shape
Microballoon, and exotic atom doping is carried out to it as the carbon-based supports of oxygen reduction catalyst using this microballoon, obtain with mesoporous and big
The hollow ball-shape oxygen reduction catalyst of the hierarchical porous structure of hole combination；This special package assembly, realizes catalytic active site
The dispersed and abundant exposure of point, and it is very beneficial for diffusion and the fast transport of oxygen, so as to accelerate its hydrogen reduction
The dynamic process of catalytic reaction.
2) oxygen reduction catalyst of the invention shows efficient hydrogen reduction chemical property and stability, and preferred oxygen is also
The half wave potential of raw catalyst its hydrogen reduction electrochemical reaction is 0.87V (vs.RHE), better than business platinum carbon (0.84V), its electricity
Chemical stability is significantly better than business platinum carbon；Zinc-air battery is assembled into, its peak power output is 248mW/cm2, it is better than
20wt% business platinum carbon (peak power outputs 198mW/cm2), its high rate performance is higher than business platinum carbon.
Description of the drawings
Fig. 1 is that the ESEM of the SWCN hollow ball assembly in embodiment 1 under different annealing temperature shines
Piece.
Fig. 2 is the transmission of the SWCN hollow ball oxygen reduction catalyst of the cobalt/nitrogen co-doped prepared by embodiment 1
Electromicroscopic photograph.
Fig. 3 is that the X of the SWCN hollow ball oxygen reduction catalyst of the cobalt/nitrogen co-doped prepared by embodiment 1 is penetrated
Photoelectron spectra figure.
Fig. 4 is the circulation of the SWCN hollow ball oxygen reduction catalyst of the cobalt/nitrogen co-doped prepared by embodiment 1
Volt-ampere curve.
Fig. 5 be the SWCN hollow ball oxygen reduction catalyst of the cobalt/nitrogen co-doped prepared by embodiment 1 and
20wt% business platinum carbons are in saturation O2Electrolyte solution (0.1M KOH) in and linear scan under 1600rpm rotating speeds it is bent
Line.
Fig. 6 is the SWCN hollow ball oxygen reduction catalyst of the cobalt/nitrogen co-doped prepared by embodiment 1 in saturation
O2Electrolyte solution (0.1M KOH) in and linear scan curve under different rotating speeds.
Fig. 7 is that the SWCN hollow ball oxygen reduction catalyst of the gained cobalt of embodiment 1/nitrogen co-doped is electric in 0.75V
Current versus time curve under position.
Fig. 8 is the polarization curve and power curve of the zinc/air fuel cell that embodiment 1 makes.
Fig. 9 is the curve of double curvature of the zinc/air fuel cell that embodiment 1 makes.
Figure 10 is the discharge curve of the zinc/air fuel cell that embodiment 1 makes.
Figure 11 is the long-time discharge curve of the zinc/air fuel cell that embodiment 1 makes.
Figure 12 is that in embodiment 2, VB12 and SWCN ball are with 1：Prepared cobalt/nitrogen is co-doped with after the mixing of 4 ratios
The cyclic voltammetry curve of miscellaneous SWCN hollow ball oxygen reduction catalyst.
Figure 13 is that in embodiment 2, VB12 and SWCN ball are with 1：Prepared cobalt/nitrogen is co-doped with after the mixing of 4 ratios
Miscellaneous SWCN hollow ball oxygen reduction catalyst is in saturation O2Electrolyte solution (0.1M KOH) in and in difference
Linear scan curve under rotary rpm.
Figure 14 is that in embodiment 2, VB12 and SWCN ball are with 1：Prepared cobalt/nitrogen is common after the mixing of 0.5 ratio
The cyclic voltammetry curve of the SWCN hollow ball oxygen reduction catalyst of doping.
Figure 15 is that in embodiment 2, VB12 and SWCN ball are with 1：Prepared cobalt/nitrogen is common after the mixing of 0.5 ratio
The SWCN hollow ball oxygen reduction catalyst of doping is in saturation O2Electrolyte solution (0.1M KOH) in and not
With the linear scan curve under rotary rpm.
Figure 16 is following for the SWCN hollow ball oxygen reduction catalyst of the iron/nitrogen co-doped prepared by embodiment 3
Ring volt-ampere curve.
Figure 17 is that the iron/nitrogen co-doped SWCN hollow ball oxygen reduction catalyst prepared by embodiment 3 is being satisfied
And O2Electrolyte solution (0.1M KOH) in and linear scan curve under different rotary rotating speed.
Figure 18 is the cyclic voltammetric of the SWCN oxygen reduction catalyst of the cobalt/nitrogen co-doped prepared by embodiment 4
Curve.
Figure 19 is the SWCN oxygen reduction catalyst of the cobalt/nitrogen co-doped prepared by embodiment 4 in saturation O2's
Linear scan curve in electrolyte solution (0.1M KOH) and under different rotary rotating speed.
Specific embodiment
Embodiment 1：
1) single dispersing aoxidizes the preparation of SWCN：
By initial SWCN solid and potassium permanganate solid with 1：The proportioning of (1～4) is together added to excess
Concentrated sulfuric acid solution in, the reaction mixture for obtaining be placed in 40-70 DEG C of water-bath continue stirring reaction 1-6h, by what is reacted
After the dilution of mixed liquor deionized water, add more than excessive hydrogen peroxide solution stirring reaction 10min, through filtering with microporous membrane with
And after the washing of dilute hydrochloric acid solution, the solid for obtaining again deionized water by high speed centrifugation wash to supernatant liquor for neutrality
(PH=6-7), then remove layer solid plus after deionized water is sufficiently stirred for, further after centrifugation, take homogeneous, stable molten in upper strata
Liquid, that is, obtain the monodispersed oxidation SWCN aqueous solution.
2) preparation of the SWCN assembly of hollow ball-shape：
First pass through ultrasound to be dispersed in water silicon dioxide microsphere template, add poly- (diallyl dimethyl ammonium chlorination
Ammonium) (PDDA) silicon dioxide microsphere template to be modified with PSS (PSS) aqueous solution so as to formation is carried
Positive charge PDDA/PSS composite modified silica ball template aqueous dispersion, then by above-mentioned modified silica spheres mould
Plate aqueous dispersion is added drop-wise in the monodispersed oxidation SWCN aqueous solution, and persistently stirs more than 0.5h, Jing Guojing
Sedimentation is put, its supernatant liquor is removed, the solid for obtaining is after 80 DEG C of oven dryings, then 500～1000 DEG C of annealing under an inert atmosphere
1-10h, finally at room temperature with 10%HF by silica etching removing, then after filtration washing and drying, obtains hollow ball
The SWCN assembly of shape.
Fig. 1 is the 1h that anneals at 500 DEG C respectively, the SWCN of the hollow ball-shape annealed under 10h at 1000 DEG C
The stereoscan photograph of assembly, as SWCN hollow ball assembly, the SWCN of the hollow ball-shape is micro-
Ball has the structure of porous.
3) preparation of Co and nitrogen co-doped SWCN hollow ball oxygen reduction catalyst：
Corproporphyrin cycle compound vitamin B12 (VB12) that Co is coordinated and the SWCN assembly of hollow ball-shape
With 1：1.5 mass ratio, by the uniform mixing of grinding, mixture is placed under 700 DEG C of ammonia atmosphere and is moved back under ethanol auxiliary
Fiery 3h, obtains the SWCN hollow ball oxygen reduction catalyst of cobalt/nitrogen co-doped, i.e. SWCN hollow ball oxygen also
Raw catalyst.
SWCN hollow ball oxygen reduction catalysts of the Fig. 2 prepared by the present embodiment, as cobalt/nitrogen co-doped
The transmission electron microscope photo of SWCN hollow ball oxygen reduction catalyst, the oxygen reduction catalyst has the combination of mesoporous and macropore
Hierarchical porous structure.
Fig. 3 is that the X of the SWCN hollow ball oxygen reduction catalyst of the cobalt/nitrogen co-doped prepared by the present embodiment is penetrated
Photoelectron spectra figure, shows that the material surface has Co and N element doping in figure.
4) making of hydrogen reduction working electrode：
5 milligrams of the sample of above-mentioned synthesis is scattered in into 2 milliliters of mass fractions is in 0.25% Nafion aqueous isopropanols,
Make material be uniformly dispersed by ultrasound, take 30 microlitres dropwise in dry rotating disk electrode (r.d.e) (diameter 5mm), after natural drying,
The electrochemical catalysis performance of test sample.
Fig. 4 is the circulation volt of the SWCN hollow ball oxygen reduction catalyst of the present embodiment gained cobalt/nitrogen co-doped
Peace curve, in saturation N20.1M KOH electrolyte solutions under, the voltage range interior circulation voltammogram of -0.03～1.15V is similar to
Rectangle, not obvious reduction peak.Comparatively, in saturation O20.1M KOH electrolyte solutions under, there is obvious oxygen
Reduction reaction (ORR) characteristic peak, illustrate this material for oxygen reduction reaction has significant electro catalytic activity, its reduction peak current is close
Degree and reduction peak voltage are respectively -5.4mA cm-2And 0.82V.
Fig. 5 is the SWCN hollow ball oxygen reduction catalyst of the present embodiment gained cobalt/nitrogen co-doped in saturation O2
Electrolyte solution (0.1M KOH) in and linear scan curve under 1600rmp rotating speeds, its half wave potential is 0.87V,
The catalyst shows the half wave potential (0.84V) higher than 20wt% business platinum carbons, illustrates that the catalyst has than business platinum
The more preferable catalysis activity of carbon.
Fig. 6 is the SWCN hollow ball oxygen reduction catalyst of the present embodiment gained cobalt/nitrogen co-doped in saturation O2
Electrolyte solution (0.1M KOH) in and linear scan curve under different rotating speeds, corresponding K outecky-levich is bent
Line shows good linear relationship in 0.4-0.7V, illustrates that complex has similar electro transfer under different voltages
Number, oxygen reduction reaction meets first-order kinetics.It is computed, its electron transfer number is between 3.93～3.99, to belong to four
Electronics accounts for leading response path, shows efficient ORR catalysis activities.
Fig. 7 is that the SWCN hollow ball oxygen reduction catalyst of the present embodiment gained cobalt/nitrogen co-doped is electric in 0.75V
Current versus time curve under position, it shows the stability more superior than business platinum carbon.After 13h is kept, still there is 96%
Electric current maintenance dose, far above business platinum carbon (81% electric current maintenance dose).
5) preparation of air electrode：
By isopropanol and 5%Nafion solution according to volume ratio 20：1 obtains mixed solution, by the hydrogen reduction of above-mentioned preparation
Catalyst ultrasonic disperse is sprayed on carbon paper or carbon cloth electrode in mixed solution, then, is dried, and obtains air electrode, is catalyzed
The carrying capacity of agent is 1mg/cm2.For the ease of comparing, using the business platinum carbon of 20wt% as catalyst, make of same step
Go out air electrode.As negative electrode, with zinc metal sheet as anode, the KOH solution of 6mol/L is electrolyte to air electrode with making, constitutes one
Individual zinc/air fuel cell, at normal temperatures and pressures respectively test obtain the polarization curve of battery, power curve, curve of double curvature and
Discharge curve.
Fig. 8 is the polarization curve and power curve of the zinc/air fuel cell that the present embodiment makes, and the list is shown in figure
The open-circuit voltage of battery is 1.51V, and maximum power density is 248mW/cm2, more than under equal conditions with 20wt% business platinum carbons
For the monocell (195mW/cm of ORR catalyst2)。
Fig. 9 be the present embodiment make zinc/air fuel cell curve of double curvature, show in figure the monocell have than
With 20wt% business platinum carbon as the more preferable high rate performance of the monocell of ORR catalyst.
Figure 10 is the discharge curve of the zinc/air fuel cell that the present embodiment makes, in 10mA/cm2And 100mA/cm2Electric current
Under density after continuous discharge 24h, voltage attenuation is respectively 0.03V and 0.07V, shows excellent continuous discharge performance and stablizes
Property.
Figure 11 is the long-time discharge curve of the zinc/air fuel cell that the present embodiment makes, in 10mA/cm2And 100mA/
cm2Discharge under current density, period changes electrolyte and zine plate, and after 48h electric discharges, voltage is only the decay within 0.01V, performance
Go out the catalyst with very excellent catalytic stability.
Embodiment 2：
Corproporphyrin cycle compound vitamin B12 (VB12) that Co is coordinated and the SWCN assembly of hollow ball-shape
Respectively with 1：4 and 1：Mixture, by the uniform mixing of grinding, is placed in 1000 DEG C by 0.5 mass ratio respectively under ethanol auxiliary
Nitrogen atmosphere under anneal 6h, obtain the SWCN hollow ball oxygen reduction catalyst of two cobalts/nitrogen co-doped, i.e. single wall
CNT hollow ball oxygen reduction catalyst
Figure 12 is that in the present embodiment, VB12 and SWCN ball are with 1：Prepared cobalt/nitrogen is co-doped with after the mixing of 4 ratios
The cyclic voltammetry curve of miscellaneous SWCN hollow ball oxygen reduction catalyst, in saturation N20.1M KOH electrolyte solutions
Under, the similar rectangle of voltage range interior circulation voltammogram of -0.03～1.15V, not obvious reduction peak.And in saturation O2's
Under 0.1M KOH electrolyte solutions, there are obvious ORR characteristic peaks, illustrate this material for ORR has electro catalytic activity, it is also
Parent peak current density and reduction peak voltage are respectively -3.5mA cm-2And 0.77V.
Figure 13 is that in the present embodiment, VB12 and SWCN ball are with 1：Prepared cobalt/nitrogen is co-doped with after the mixing of 4 ratios
Miscellaneous SWCN hollow ball oxygen reduction catalyst is in saturation O2Electrolyte solution (0.1M KOH) in and in difference
Linear scan curve under rotary rpm, half wave potential under the 1600rmp rotating speeds of the catalyst is 0.82V, and platinum carbon connects
Closely, illustrate that the catalyst has good ORR catalysis activities.
Figure 14 is that in the present embodiment, VB12 and SWCN ball are with 1：Prepared cobalt/nitrogen is common after the mixing of 0.5 ratio
The cyclic voltammetry curve of the SWCN hollow ball oxygen reduction catalyst of doping, in saturation O20.1M KOH electrolyte it is molten
Under liquid, there are obvious ORR characteristic peaks, illustrate that this material equally has an ORR electro catalytic activities, its reduction peak current density and also
Parent peak voltage is respectively -4.0mA cm-2And 0.80V.
Figure 15 is that in the present embodiment, VB12 and SWCN ball are with 1：Prepared cobalt/nitrogen is common after the mixing of 0.5 ratio
The SWCN hollow ball oxygen reduction catalyst of doping is in saturation O2Electrolyte solution (0.1M KOH) in and not
With the linear scan curve under rotary rpm, half wave potential of the catalyst under 1600rmp rotating speeds is 0.84V, and 20wt%
Being close to for business platinum carbon, illustrates that the catalyst has good ORR catalysis activities.
Can draw from the present embodiment：Precursor compound containing transition metal and nitrogen mixes with carbon carrier in different proportion
Under, the catalyst for obtaining still has good oxygen reduction catalytic activity；Additionally, except annealing under ammonia atmosphere, in inertia
Annealing obtains catalyst and remains on good oxygen reduction catalytic activity (under nitrogen, argon gas) under atmosphere.
Embodiment 3：
The corproporphyrin cycle compound hydroxyl oxygen protoferriheme that Fe is coordinated and the SWCN assembly of hollow ball-shape
Respectively with 1：Mixture, by the uniform mixing of grinding, is placed in 1000 DEG C of ammonia gas by 0.5 mass ratio under ethanol auxiliary
Anneal 1h under atmosphere, obtains the SWCN hollow ball oxygen reduction catalyst of iron/nitrogen co-doped, i.e. SWCN is hollow
Ball oxygen reduction catalyst.
Figure 16 is the circulation volt of the SWCN hollow ball oxygen reduction catalyst of the present embodiment gained iron/nitrogen co-doped
Peace curve, in saturation N20.1M KOH electrolyte solutions under, the voltage range interior circulation voltammogram of -0.03～1.15V is similar to
Rectangle, not obvious reduction peak.Comparatively, in saturation O20.1M KOH electrolyte solutions under, there is obvious oxygen
Reduction reaction (ORR) characteristic peak, illustrate this material for oxygen reduction reaction has significant electro catalytic activity, its reduction peak current is close
Degree and reduction peak voltage are respectively -3.2mA cm-2And 0.79V.
Figure 17 is that the iron/nitrogen co-doped SWCN hollow ball oxygen reduction catalyst prepared by the present embodiment is being satisfied
And O2Electrolyte solution (0.1M KOH) in and linear scan curve under different rotary rotating speed, the catalyst
Half wave potential under 1600rmp rotating speeds be 0.83V, and 20wt% business platinum carbons be close to, illustrate with Fe coordination corproporphyrin ring
Compound also has good ORR catalysis activities as the catalyst that doping presoma is obtained.
Embodiment 4
The monodisperse single-walled carbon nanotube aqueous solution prepared by embodiment 1 is collected by filtration, and the SWCN for obtaining is consolidated
After body drying drying, with VB12 with 1：1.5 mass ratio mixes under ethanol auxiliary by the way that grinding is uniform, respectively by mixture
The 3h that anneals is placed under 700 DEG C of nitrogen atmosphere, the SWCN oxygen reduction catalyst of cobalt/nitrogen co-doped is obtained.
Figure 18 is that the cyclic voltammetric of the SWCN oxygen reduction catalyst of the present embodiment gained cobalt/nitrogen co-doped is bent
Line, in saturation N20.1M KOH electrolyte solutions under, the similar rectangle of the voltage range interior circulation voltammogram of -0.03～1.15V,
Not obvious reduction peak.Comparatively, in saturation O20.1M KOH electrolyte solutions under, there is obvious hydrogen reduction anti-
Answer (ORR) characteristic peak, illustrate this material for oxygen reduction reaction has significant electro catalytic activity, its reduction peak current density and also
Parent peak voltage is respectively -3.5mA cm-2And 0.77V.
Figure 19 is the SWCN oxygen reduction catalyst of the present embodiment gained cobalt/nitrogen co-doped in saturation O2Electrolysis
Linear scan curve in matter solution (0.1M KOH) and under different rotating speeds, the oxygen reduction reaction under 1600rmp rotating speeds
Half wave potential is 0.82V, is close to 20wt% business platinum carbon, illustrates that the catalyst has good catalysis activity.
Claims (8)
1. a kind of preparation method of SWCN hollow ball oxygen reduction catalyst, the SWCN hollow ball oxygen is also
Raw catalyst is transition metal and nitrogen co-doped SWCN hollow ball oxygen reduction catalyst, first will be single with hard template method
Dispersion oxidation SWCN is self-assembled into the SWCN ball of hollow ball-shape, then by SWCN hollow ball with
Transition metal N4 cycle compounds are sufficiently mixed, and then calcining realizes that transition metal and nitrogen are co-doped with ammonia or inert atmosphere
It is miscellaneous, obtain SWCN hollow ball oxygen reduction catalyst；
Comprise the following steps：
(1) single dispersing aoxidizes the preparation of SWCN；
(2) preparation of the SWCN assembly of hollow ball-shape；
(3) preparation of transition metal and nitrogen co-doped SWCN hollow ball oxygen reduction catalyst；
Described transition metal and the preparation of nitrogen co-doped SWCN hollow ball oxygen reduction catalyst, walk including following
Suddenly：
By the SWCN assembly of transition metal N4 cycle compounds and hollow ball-shape with 1：The ratio uniform of (0.5～4)
Mixing, by mixture be placed under 700 DEG C -1000 DEG C of inert atmosphere or under ammonia atmosphere anneal 1～6h, obtain transition metal with
Nitrogen co-doped SWCN hollow ball, that is, obtain SWCN hollow ball oxygen reduction catalyst.
2. method according to claim 1, it is characterised in that described single dispersing aoxidizes the preparation side of SWCN
Method, comprises the following steps：
By initial SWCN solid and potassium permanganate solid with 1：The proportioning of (1～4) is together added to excessive dense
In sulfuric acid solution, the reaction mixture for obtaining is placed in 40-70 DEG C of water-bath and continues stirring reaction 1-6h, by the mixing reacted
After the dilution of liquid deionized water, excessive hydrogen peroxide solution stirring more than 10min is added, then through filtering with microporous membrane and dilute salt
After the washing of acid solution, the solid for obtaining again deionized water by high speed centrifugation wash to supernatant liquor be neutrality (PH=6-
7), then remove layer solid plus after deionized water is sufficiently stirred for, further after centrifugation, take homogeneous, the stable solution in upper strata, obtain final product
To the monodispersed oxidation SWCN aqueous solution.
3. method according to claim 1, it is characterised in that the SWCN assembly of described hollow ball-shape
Preparation, comprise the following steps：
Silicon dioxide microsphere template is dispersed in water by ultrasound, is added poly- (diallyl dimethyl ammonium ammonium chloride)
(PDDA) silicon dioxide microsphere template is modified with PSS (PSS) aqueous solution so as to formed with just
Electric charge PDDA/PSS composite modified silica ball template aqueous dispersion, then by above-mentioned modified silica ball template
Aqueous dispersion is added drop-wise in the monodispersed oxidation SWCN aqueous solution, and persistently stirs more than 0.5h, through standing
Sedimentation, removes its supernatant liquor, and the solid for obtaining is after 80 DEG C of oven dryings, then 500 DEG C of -1000 DEG C of annealing 1- under an inert atmosphere
10h, finally at room temperature with 10%HF by silica etching removing, then after filtration washing and drying, obtains hollow ball-shape
SWCN assembly.
4. method according to claim 1, it is characterised in that described transition metal N4 cycle compounds are that Fe or Co is coordinated
Corproporphyrin ring complex in it is a kind of.
5. the method according to claim 1 and 3, it is characterised in that described inert atmosphere is nitrogen, argon gas or helium gas
Atmosphere.
6. the application of SWCN hollow ball oxygen reduction catalyst, it is characterised in that the SWCN hollow ball
Oxygen reduction catalyst is transition metal and nitrogen co-doped SWCN hollow ball oxygen reduction catalyst, and it is applied to hydrogen-oxygen
The air electrode catalyst of fuel cell, zinc/air fuel cell, magnesium air fuel cell or aluminium air-fuel battery.
7. application according to claim 6, it is characterised in that the preparation method of described air electrode：By isopropanol and
5%Nafion solution is according to volume ratio (10～20)：1 obtains mixed solution, by SWCN hollow ball hydrogen reduction catalysis
Agent is distributed in mixed solution, ultrasound, is sprayed on carbon paper or carbon cloth electrode, is dried, and obtains air electrode.
8. the SWCN oxygen for being prepared using preparation method described in claims 1 to 3 any one claim is also
Raw catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710113602.1A CN106602092B (en) | 2017-02-28 | 2017-02-28 | Preparation method and application of single-walled carbon nanotube hollow sphere oxygen reduction catalyst |
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| CN108695522A (en) * | 2018-05-29 | 2018-10-23 | 湖南科技大学 | A kind of preparation method of NEUTRAL ALUMINUM-O for cathode of air battery material and application |
| CN109465033A (en) * | 2017-09-08 | 2019-03-15 | 梅玉杰 | A kind of preparation method for the carbon nano tube air purifier removing formaldehyde |
| CN110690458A (en) * | 2019-08-23 | 2020-01-14 | 安徽力普拉斯电源技术有限公司 | Preparation method and application of bamboo-shaped carbon nanotube oxygen reduction electrocatalyst |
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| CN113314719A (en) * | 2021-04-09 | 2021-08-27 | 国联汽车动力电池研究院有限责任公司 | Integrated cathode with high catalytic performance, preparation method thereof and battery |
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| WO2022095492A1 (en) * | 2020-11-04 | 2022-05-12 | 江苏科技大学 | High-performance metal-air cell positive electrode catalyst and preparation method therefor |
| US11658310B2 (en) | 2020-11-04 | 2023-05-23 | Jiangsu University Of Science And Technology | High-performance cathode catalyst for metal-air battery and preparation method thereof |
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| CN114188557A (en) * | 2021-10-29 | 2022-03-15 | 陕西师范大学 | Preparation method and application of multi-mesoporous transition metal-nitrogen-carbon catalyst |
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