CN108923051A - A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application - Google Patents
A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application Download PDFInfo
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- CN108923051A CN108923051A CN201810734545.3A CN201810734545A CN108923051A CN 108923051 A CN108923051 A CN 108923051A CN 201810734545 A CN201810734545 A CN 201810734545A CN 108923051 A CN108923051 A CN 108923051A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its applications, belong to battery material field.The composite catalyst is with dicyandiamide class cobalt-based metal-organic framework materials（Co(dca)2pyz）It for presoma, was only carbonized under nitrogen atmosphere by three hours, is used for efficient electric catalytic oxidation-reduction.In 0.1 mol L‑1Potassium hydroxide electrolyte in, the hydrogen reduction half wave potential of the catalyst is 0.82 V, and limiting diffusion current is 5.3 mA cm‑2.Pass through the cyclic charging and discharging test of 65 h with the zinc and air cell that prepared catalyst assembles, charging/discharging voltage difference shows that prepared catalyst has very strong stability, have higher practical application value there is no significantly changing.
Description
Technical field
The present invention relates to composite catalyst, belong to battery material field, and in particular to a kind of package metals cobalt nano-particle
Nitrogen-doped carbon nanometer pipe composite catalyst and preparation method thereof and its answering in electrocatalytic oxidation reduction reaction and zinc-air battery
With.
Background technique
It is increasingly serious with energy crisis and problem of environmental pollution, the chemical energy of fuel is directly changed into cleaning electric energy
Electrochemical energy conversion devices become one huge challenge of 21 century.Wherein, zinc-air battery technology because its high-energy it is close
Degree, environment friendly, safety and low cost arouse widespread concern.Since zinc-sky battery directly utilizes in air
Oxygen as cathode active material, therefore, the catalyst of air cathode redox reactions be the key that determine battery performance
Factor.But the hysteresis quality of cathodic oxygen reduction reaction rate promotes the elctro-catalyst of scientists exploitation efficient stable to overcome this
One disadvantage.So far, precious metal material (such as：Platinum, palladium etc.) be most effective electrocatalytic oxidation reducing catalyst, but its at
The characteristics such as this is high, reserves are limited, stability is poor strongly limit large-scale commercial use of the catalyst in clean energy resource.Cause
This, it is most important to the practical application of zinc-air battery to develop cheap, efficient, durable oxygen reduction electro-catalyst.
Since nineteen nineties, since Yaghi defines metal organic frame (MOFs) for the first time, MOFs is due to its fan
The structure and performance of people cause the extensive concern of scientists.Recently, MOFs is since height crystallization, porosity and composition can
The various features such as tune are widely deployed sacrifice template and presoma certainly for constructing carbon material.Nano material derived from MOFs,
Generally have many advantages, such as high-specific surface area, porosity, function controllability, in multiple fields such as electro-catalysis, photocatalysis, fuel cells
Show tempting application prospect.
In recent years, due to high conductivity and stability, transition metal is compound with nitrogen-doped carbon nanometer pipe (NCNT) hydridization
Profile material is expected to become a kind of elctro-catalyst of substitution precious metal material.Currently, researchers are dedicated to studying effective strategy
To synthesize this hybrid material, such as arc discharge, laser ablation and chemical vapor deposition.Due to harsh synthesis condition, carbon
The preparation of nanotube hybrid material is a very big problem.Therefore, develop a kind of mild efficient synthetic strategy, for transition gold
Belong to and being very important with the practical application of carbon nano-tube hybridization material.Wherein directly pyrolysis MOF be a kind of synthesis high yield with
The effective method of accurate doped carbon nanometer pipe.Carbon is obtained in a mild condition as single presoma using metal framework material to receive
The research of nanotube material is also fewer.Therefore, it is compound efficiently to prepare transition metal/nitrogen-doped carbon nanometer pipe by exploitation novelty MOF
Catalyst has important practical significance to the research and development for promoting catalyst in the field.
Summary of the invention
The purpose of the present invention is to provide a kind of compound catalysis of nitrogen-doped carbon nanometer pipe of package metals cobalt nano-particle
Agent is (referred to as：Co@NCNTs), realize its cheap, efficient, durable application effect in electrocatalytic reaction and zinc-air battery
Fruit.
To achieve the purpose of the present invention, the present invention selects two kinds of containing n-donor ligands of dicyandiamide sodium and pyrazine cheap and easy to get and can
The three-dimensional cobalt-based metal-organic framework materials (Co (dca) that dissolubility cobalt salt is constructed2It pyz) is the compound electro-catalysis of precursor preparation
Oxygen reduction catalyst (Co@NCNTs) is used for electrocatalytic reaction and zinc-air battery.
The nitrogen-doped carbon nanometer pipe composite catalyst is prepared via a method which：
(1) dicyandiamide sodium, pyrazine, soluble cobalt are dissolved in hot water respectively, are stirred at room temperature, is uniformly mixed, reaction
After, obtain turbid solution.
(2) turbid solution obtained in step (1) is filtered, washs filtering repeatedly with deionized water, obtains solid powder,
Obtain Co (dca) after drying2Pyz presoma.
(3) under nitrogen atmosphere by step (2) resulting Co (dca)2The calcining of pyz presoma, gained powder is through dilute sulfuric acid
Then supersound washing is centrifuged repeatedly washing with deionized water and ethyl alcohol and obtains object for several times, after drying.
The soluble cobalt selects cobalt nitrate, cobalt chloride, cobaltous sulfate etc..
The molar ratio of dicyandiamide sodium, pyrazine and soluble cobalt is 2-3 in step (1)：1：1.
The temperature of step (3) presoma calcining is 700-1000 DEG C, and heating rate is 10 DEG C/min.
It is applied the composite material as catalyst in terms of electrocatalytic reaction and zinc-air battery.
Above-mentioned application method is as follows：1. electrocatalytic oxidation reduction reaction is mixed with the nitrogen of prepared package metals cobalt nano-particle
Miscellaneous carbon nanotube compound material is the catalyst of working electrode, is used for its catalytic oxidation-reduction reactivity worth using three-electrode system
Test.It take reference electrode, platinum filament as auxiliary electrode of silver-silver chloride (Ag/AgCl) electrode, potassium hydroxide aqueous solution is electrolysis
Liquid, preferably 0.1mol L-1。
2. zinc-air battery is tested：Nitrogen-doped carbon nanometer pipe compound material with prepared package metals cobalt nano-particle is
Catalyst, which is coated in nickel foam, is used as anode, and it is diaphragm among positive and negative anodes that polishing zine plate, which is cathode, and anode connects with air
Touching side is air diffusion layer, and electrolyte is 6mol L-1Potassium hydroxide aqueous solution and 0.2mol L-1Zinc acetate aqueous solution.
The invention has the advantages that：The electrocatalytic oxidation reducing material is with three-dimensional cobalt-based metal-organic framework materials (Co
(dca)2It pyz) is presoma, the nitrogen-doped carbon nanometer pipe for forming cladding metal cobalt nano-particle by carbonation step is compound to urge
Agent.Dicyandiamide can crack to form g-C at high temperature3N4, it is the common presoma of N doping graphitic carbon nano material.In addition,
MOF and dicyandiamide mixing, which help to be obtained, crosses metal/carbon nanotube hybrid material.Based on this, we select dicyandiamide fund
Belong to organic framework materials as single presoma, in lower temperature (down to 700 degree), short period (three hours), nitrogen atmosphere
The compound material of nitrogen-doped carbon nanometer pipe cladding metallic cobalt can be prepared down.The carbon nano-tube hybridization material has high ratio
Surface area, micropore, mesoporous, macropore and the multistage pore property deposited.These design features can expose more active sites, simultaneously
Promote the transport of reactants and products in electro-catalysis conversion process of energy.On the other hand, mixing nitrogen heteroatom in carbon nanotube can
It is electronic-controlled to cause, a large amount of defects are caused in nanotube walls, to generate positive charge on adjacent carbon atom, are provided additional
Active site.The two complements each other, and further improves the electro catalytic activity of on-target hybrid material, can be applied to electro-catalysis
Oxygen reaction and zinc-air battery research field, have important value and realistic meaning.It is tested through experiment, prepared by the present invention
The ability that catalyst has stability more better than platinum carbon catalyst and has extraordinary methanol tolerance to poison.It is restored in electrocatalytic oxidation
In, catalytic effect is similar compared with the noble metal catalysts such as platinum carbon, half wave potential 0.82V, and limiting diffusion current is
5.3mA cm-2.In zinc-air battery application, current density is 10 and 100mA cm-2When, cell voltage is respectively 1.20 Hes
0.82V, battery maximum power density are 90mW cm-2.There is preferable application effect compared to current noble metal catalyst.Simultaneously
Also new thinking is provided for the preparation of other carbon nano tube compound materials.
Detailed description of the invention
Fig. 1 is Co (dca) synthesized in step (1)2Powder x-ray diffraction (PXRD) map and list of pyz presoma
Crystalline substance simulation PXRD map comparison diagram；Wherein, the 1 PXRD spectrum to be simulated by single crystal data；2 be presoma Co (dca) of the present invention2The PXRD of pyz is composed.It can be seen that the presoma purity is high of preparation, good crystallinity.
Fig. 2 is powder x-ray diffraction (PXRD) map of catalyst Co@NCNTs prepared by the present invention, wherein 1 is vertical
The PXRD spectrum that prismatic crystal system Co standard card is simulated；2 compose for the PXRD of catalyst Co@NCNTs prepared by the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph (a, b) that catalyst prepared by the present invention amplifies different multiples.
Fig. 4 is the transmission electron microscope picture of catalyst prepared by the present invention, and figure a is high-resolution-ration transmission electric-lens figure, wherein 1 is carbon
Nanotube layer, 2 be the lattice diffraction fringe of the cobalt nano-particle coated by graphite carbon-coating.Figure b is selective electron diffraction map, figure
C-f is that first vegetarian noodles transmits (mapping) electron microscope.
Fig. 5 is nitrogen adsorption isotherm of catalyst at a temperature of 77K prepared by the present invention, and illustration is according to absorption etc.
The pore size distribution curve for the catalyst that warm line computation goes out.
Fig. 6 is the 0.1mol L that catalyst Co@NCNTs prepared by the present invention is saturated in oxygen-1In potassium hydroxide solution
Cyclic voltammetry curve.1 is nitrogen atmosphere in figure, and 2 be oxygen atmosphere.
Fig. 7 is the 0.1mol L that catalyst prepared by the present invention is saturated in oxygen under different calcination temperatures-1Potassium hydroxide
Linear sweep voltammetry curve in solution, rotating disk electrode (r.d.e) revolving speed are 1600 revs/min.In figure 1 be 1000 DEG C of calcination temperatures, 2
It is 20% platinum carbon catalyst of mass percentage for 800 DEG C of calcination temperatures, 3,4 be 900 DEG C of calcination temperatures.
Fig. 8 is catalyst prepared by the present invention and the 0.1mol L that platinum carbon is saturated in oxygen-1It is steady in potassium hydroxide solution
Qualitative test comparison, rotating disk electrode (r.d.e) revolving speed are 1600 revs/min, wherein 1 is catalyst prepared by the present invention, and 2 be quality
20% platinum carbon catalyst of percentage composition.
Fig. 9 is catalyst prepared by the present invention and the 0.1mol L that platinum carbon is saturated in oxygen-1In potassium hydroxide solution
Methanol tolerance poisons aptitude tests, and rotating disk electrode (r.d.e) revolving speed is 1600 revs/min.Wherein, 1 for the present invention prepared by catalyst, 2
It is the addition 3mol L into system for 20% platinum carbon catalyst of mass percentage, 3-1Methanol.
Figure 10 is zinc and air cell schematic device, in figure, 1- zine plate (cathode), and 2-Co@NCNTs (anode), 3- electrolyte,
4- oxygen, 5- gas diffusion layers.
Figure 11 be assembled using catalyst prepared by the present invention as positive electrode zinc and air cell electric discharge polarization curve and
Power density curve.
Figure 12 is the zinc and air cell cyclical stability test assembled using catalyst prepared by the present invention as positive electrode,
Charging and discharging currents density is 5mA cm-2。
Specific embodiment
Below by example, the present invention is described further：
Embodiment 1：Synthesize the nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle.
(1) 0.38g cobalt nitrate is dissolved in 20mL90 DEG C of deionized water, 0.096g dicyandiamide sodium and the dissolution of 0.2g pyrazine
In 90 DEG C of deionized waters of 20mL, the two is uniformly mixed, and is stirred 30min at room temperature and is obtained pink colour turbid solution.Through filtering, water
It washes, presoma (Co (dca) is obtained after vacuum drying2Pyz) pink solid powder.
(2) pink solid powder will be obtained in 500mg step (1) to be placed in quartz boat, quartz boat is placed on tube furnace
Interior, logical nitrogen 30min exhausts furnace air in advance, and then tube furnace is warming up under nitrogen atmosphere with the rate of 10 DEG C/min
900 DEG C, and in 900 DEG C of calcining at constant temperature 3h.Cooled to room temperature, obtained black porous solid through dilute sulfuric acid supersound washing,
Then washing is centrifuged repeatedly for several times with deionized water and ethyl alcohol, black solid powder is obtained after drying and grinding.As final catalyst
(Co@NCNTs)。
Embodiment 2：The nitrogen-doped carbon nanometer pipe compound material of package metals cobalt nano-particle prepared by the present invention is made
For the performance test of elctro-catalyst.
2mg Co@NCNTs catalyst of the present invention is added in 150uL isopropanol and the mixed solution of 150uL deionized water,
The Nafion solution that 20uL mass percent is 5% is added, finely dispersed black catalyst slurry is obtained after ultrasonic disperse 30min
Liquid.10uL slurry drops are coated in rotating disk electrode (r.d.e) and are dried at room temperature for.Electrocatalysis characteristic test uses three-electrode system,
It take reference electrode, platinum filament as auxiliary electrode, 0.1mol L of silver-silver chloride (Ag/AgCl) electrode-1Potassium hydroxide aqueous solution is electricity
Solve liquid.Test equipment is Pine company Wavedriver10 constant potential/electric current instrument, MSR rotating disk electrode (r.d.e) device.
As shown in fig. 6, the 0.1mol L with nitrogen saturation-1Cyclic voltammogram in potassium hydroxide solution is compared, in oxygen
Prepared catalyst has obviously oxygen reduction peak under conditions of saturation, it was demonstrated that the material has an excellent hydrogen reduction
Performance.
As shown in fig. 7, in the 0.1mol L of oxygen saturation-1In potassium hydroxide solution, electrode revolving speed is 1600 revs/min of item
Under part, the catalyst that different carburizing temperatures obtain has apparent oxygen reduction electric current.Wherein be carbonized at 900 DEG C obtained catalysis
Agent has best electrocatalytic oxidation reducing property, the catalytic effect class with noble metal catalyst (platinum carbon, mass fraction 20%)
Seemingly, half wave potential 0.82V, limiting diffusion current are 5.3mA cm-2。
As shown in figure 8, in the 0.1mol L of oxygen saturation-1In potassium hydroxide solution, electrode revolving speed is 1600 revs/min of item
Under part, catalyst prepared by the present invention has stability more better than platinum carbon catalyst.
As shown in figure 9, in the 0.1mol L of oxygen saturation-1In potassium hydroxide solution, electrode revolving speed is 1600 revs/min of item
Under part.When methanol is added into system, the catalytic current of platinum carbon catalyst is substantially reduced, and catalyst prepared by the present invention
Catalytic current does not change substantially other than by slight interference, illustrates compared with noble metal catalyst, prepared by the present invention
The catalyst ability that there is extraordinary methanol tolerance to poison.
Embodiment 3：The nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle prepared by the present invention
Application in zinc and air cell.
In conjunction with Figure 10 zinc and air cell schematic device.Cathode is zine plate, and anode is load prepared catalyst of the present invention
Nickel foam.Electrolyte is 6mol L-1Potassium hydroxide aqueous solution and 0.2mol L-1Zinc acetate aqueous solution, by diaphragm between positive and negative anodes
It separates, it is gas diffusion layers that anode, which contacts one side with air,.
Figure 11 is the polarized discharge curve and corresponding power of the zinc and air cell device assembled with prepared catalyst
Densogram, current density are 10 and 100mA cm-2When, cell voltage is respectively 1.20 and 0.82V, and battery maximum power is close
Degree is 90mW cm-2。
As shown in figure 12, the cycle charge-discharge of 65h is passed through with the zinc and air cell that prepared catalyst of the present invention assembles
Test, charging/discharging voltage difference show that prepared catalyst has very strong stability there is no significantly changing, have compared with
High practical application value.
Claims (5)
1. a kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle, which is characterized in that by as follows
Method is prepared：
（1）Dicyandiamide sodium, pyrazine, soluble cobalt are dissolved in hot water respectively, stirred evenly, is reacted at room temperature, after reaction,
Obtain turbid solution；
（2）By step（1）Obtained in turbid solution filtering, washed repeatedly with deionized water, obtain solid powder, after drying
It obtains Co (dca)2Pyz presoma；
（3）Under nitrogen atmosphere by step（2）Resulting Co (dca)2The calcining of pyz presoma, gained powder are washed through dilute sulfuric acid ultrasound
It washs, is then centrifuged repeatedly washing with deionized water and ethyl alcohol, obtains target product Co NCNTs after dry.
2. the nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle as described in claim 1, feature exist
In the soluble cobalt is any one of cobalt nitrate, cobalt chloride, cobaltous sulfate.
3. the nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle as claimed in claim 1 or 2, feature
It is,
Step（1）The molar ratio of middle dicyandiamide sodium, pyrazine and soluble cobalt is 2-3：1：1；
Step（3）The temperature of presoma calcining is 700-1000 DEG C, and heating rate is 10 DEG C/min.
4. the nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle as described in one of claim 1-3
Application, which is characterized in that it is as follows as elctro-catalyst working electrode application method：
（1）Isopropanol is added in the nitrogen-doped carbon nanometer pipe composite catalyst Co@NCNTs of package metals cobalt nano-particle and is gone
In the mixed solution of ionized water, Nafion solution is added, obtains finely dispersed catalyst slurry after ultrasonic disperse；By catalyst
Slurry drops are coated in rotating disk electrode (r.d.e) and are dried at room temperature for；（2）Using three-electrode system, with silver-silver chloride (Ag/AgCl)
Electrode is reference electrode, platinum filament is auxiliary electrode, and potassium hydroxide aqueous solution is electrolyte.
5. the nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle as described in one of claim 1-3
Application, which is characterized in that it is as follows as zinc-air battery application method：
The nitrogen-doped carbon nanometer pipe composite catalyst Co@NCNTs of package metals cobalt nano-particle is coated in nickel foam and is made
For anode, it is diaphragm among positive and negative anodes that zine plate, which is cathode, and anode is air diffusion layer, electrolyte with air contact side
For potassium hydroxide and zinc acetate aqueous solution.
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