CN110451489A - A kind of cobalt nitride is embedded in porous nitrogen-doped graphene material and preparation method and application - Google Patents
A kind of cobalt nitride is embedded in porous nitrogen-doped graphene material and preparation method and application Download PDFInfo
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Abstract
Present disclose provides a kind of cobalt nitrides to be embedded in porous nitrogen-doped graphene material and preparation method and application comprising nitrogen-doped graphene and Co5.47There are the cavernous structure of vermiform trace, Co in N nano particle, the nitrogen-doped graphene surface5.47N nano particle is embedded in the end of the cavernous structure of vermiform trace.Preparation method are as follows: sequentially add the uniformly mixed acquisition suspension of cobalt acetate, tannic acid into the dispersion liquid of graphene oxide, after the solid material in suspension is separated, be heated to being pyrolyzed not less than 600 DEG C under nitrogen and ammonia gas mixture atmosphere.The material that the disclosure provides shows effective multi-functional catalytic activity to ORR, HER and OER in alkaline solution.
Description
Technical field
The disclosure belongs to electrochemical field, is related to elctro-catalyst, and in particular to a kind of porous N doping stone of cobalt nitride insertion
Black alkene material and preparation method and application.
Background technique
Here statement only provides background information related with the disclosure, without necessarily constituting the prior art.
A large amount of consumption of conventional fossil fuel lead to serious weather and environmental problem, and which results in people to clean exploitation
The concern, such as fuel cell, metal-air battery and electrolytic water device etc. of efficient electrochemical energy conversion and storing technology.
These energy stores and the performance of conversion equipment are determined by several basic electrochemical reactions.For example, chargeable zinc-air battery
It is received more and more attention because of its at low cost, environmental-friendly and theoretical energy density high the advantages that.Oxygen evolution reaction
(OER) and redox reactions (ORR) are two crucial half-reactions, decide the final performance of zinc-air battery.In addition, electric
Xie Shui mainly includes that hydrogen evolution reaction (HER) reacts (OER) with oxygen evolution, this is to obtain cleaning Hydrogen Energy to have very much prospect
Method.Due to the multielectron transfer process and slow dynamics of ORR, OER and HER, efficient elctro-catalyst is needed to reduce
Reaction overpotential simultaneously improves transformation efficiency.So far, unifunctional OER ORR elctro-catalyst has made important progress.Example
Such as, platinum (Pt) and its alloy-based catalyst are effective ORR/HER catalyst, and ruthenium (Ru)/iridium (Ir) and its oxide represent
OER state-of-the-art catalyst material.However, this noble metal-based catalysts reserves have according to known to the disclosed invention people research
Limit, at high cost, stability is poor, and generally can not be used as the multi-functional elctro-catalyst of ORR, HER and OER simultaneously.
Summary of the invention
In order to solve the deficiencies in the prior art, purpose of this disclosure is to provide a kind of cobalt nitrides to be embedded in porous N doping graphite
Alkene material and preparation method and application, the material show effective multi-functional catalysis to ORR, HER and OER in alkaline solution
Activity.
To achieve the goals above, the technical solution of the disclosure are as follows:
In a first aspect, present disclose provides a kind of cobalt nitrides to be embedded in porous nitrogen-doped graphene material, including N doping stone
Black alkene and Co5.47There are the cavernous structure of vermiform trace, Co in N nano particle, the nitrogen-doped graphene surface5.47N nano particle
It is embedded in the end of the cavernous structure of vermiform trace.
Co in the material that the disclosure provides5.47N nano particle is embedded in the end of the cavernous structure of vermiform trace, can be with
Promote the quick interface electronics transfer and ion diffusion of respective reaction, while the poly- of nitridation cobalt nano-particle can be effectively inhibited
Collection and crushing, so that the material of the disclosure shows effective multi-functional catalysis to ORR, HER and OER in alkaline solution
Activity.
Second aspect, present disclose provides the preparation method that a kind of cobalt nitride is embedded in porous nitrogen-doped graphene material, to
The uniformly mixed acquisition suspension of cobalt acetate, tannic acid is sequentially added in the dispersion liquid of graphene oxide, by the solid in suspension
After feed separation comes out, it is heated to being pyrolyzed not less than 600 DEG C under nitrogen and ammonia gas mixture atmosphere.
There are benzene ring structures for tannic acid in the disclosure, and the electrostatic interaction of pi-pi accumulation can be formed with graphene oxide,
The combination for enabling tannic acid stable on graphene oxide, while tannic acid there are phenolic hydroxyl groups can be with Co2+Ion chelating
Form five yuan of stable chelate rings, and then can be by tannic acid by Co2+Ion is dispersed to surface of graphene oxide.Secondly, logical
Co could be embedded in by the above method on nitrogen-doped graphene by crossing experiment discovery only cobalt acetate5.47N, and other cobalt salts,
Such as cobalt chloride, cobalt nitrate, cobaltous sulfate etc., Co can not be embedded on nitrogen-doped graphene5.47N.Third, the preparation of the disclosure
Method can make the Co to be formed5.47Thermal etching movement of the N nanoparticle on redox graphene surface, which will lead to, to be nitrogenized
Vermiform hole is formed in the process, this will generate more surface defects to enhance electro catalytic activity.
The third aspect, present disclose provides a kind of above-mentioned cobalt nitrides to be embedded in porous nitrogen-doped graphene material in metal-air
Application in field of batteries and/or electrolysis water.
Fourth aspect, present disclose provides a kind of electrode materials, including above-mentioned cobalt nitride to be embedded in porous nitrogen-doped graphene
Material.
5th aspect, present disclose provides a kind of zinc-air batterys, are embedded in porous nitrogen-doped graphene with above-mentioned cobalt nitride
Material is as air cathode.
6th aspect, present disclose provides a kind of elctro-catalyst, active constituent is that above-mentioned cobalt nitride is embedded in porous N doping
Grapheme material.
7th aspect, present disclose provides a kind of methods of electrolysis water, are embedded in porous N doping graphite with above-mentioned cobalt nitride
Alkene material uses zinc-air battery by water decomposition for hydrogen and oxygen as elctro-catalyst.
The disclosure has the beneficial effect that
The preparation method of the disclosure is being layered porous rGO on piece fabricated in situ Co5.47N nano particle, Co5.47N nanoparticle
Be formed in situ and cause to form vermiform channel and hole on the surface rGO with warm-up movement etching.The material pair of disclosure preparation
ORR, HER and OER have outstanding electro catalytic activity, can manufacture chargeable zinc-air battery.The zinc-air battery of preparation
High power density (120.7mWcm when with high open circuit potential (1.45V), 0.67V-2), excellent cycling more than 330h stablizes
Property and good rechargeable performance.In addition, the material using the disclosure carries out electrolysis water, there is good the rate of gas production.
Detailed description of the invention
The Figure of description for constituting a part of this disclosure is used to provide further understanding of the disclosure, and the disclosure is shown
Meaning property embodiment and its explanation do not constitute the improper restriction to the disclosure for explaining the disclosure.
Fig. 1 is Co prepared by the embodiment of the present disclosure 35.47The electromicroscopic photograph of N@N-rGO-750, a are scanning electron microscope, and b is
Radio mirror；
Fig. 2 is the Co that the embodiment of the present disclosure 1,2,4 is prepared respectively5.47N@N-rGO-650、Co5.47N@N-rGO-700、
Co5.47The electromicroscopic photograph of N@N-rGO-800, a Co5.47The stereoscan photograph of N@N-rGO-650, b Co5.47N@N-rGO-
650 stereoscan photograph, c Co5.47The transmission electron microscope photo of N@N-rGO-650, d Co5.47The scanning of N@N-rGO-700
Electromicroscopic photograph, e Co5.47The stereoscan photograph of N@N-rGO-700, f Co5.47The transmission electron microscope photo of N@N-rGO-700, g
For Co5.47The stereoscan photograph of N@N-rGO-800, h Co5.47The stereoscan photograph of N@N-rGO-800, i Co5.47N@
The transmission electron microscope photo of N-rGO-800；
Fig. 3 is Co prepared by the embodiment of the present disclosure 1~45.47N@N-rGO-650、Co5.47N@N-rGO-700、Co5.47N@N-
rGO-750、Co5.47The XRD spectrum of N@N-rGO-800；
Fig. 4 is Co prepared by the embodiment of the present disclosure 55.47The stereoscan photograph of N@N-rGO-750-2h；
Fig. 5 is Co prepared by the embodiment of the present disclosure 65.47The stereoscan photograph of N@N-rGO-750-3h；
Fig. 6 is Co prepared by the embodiment of the present disclosure 5,65.47N@N-rGO-750-2h、Co5.47The XRD of N@N-rGO-750-3h
Map；
Fig. 7 is Co prepared by the embodiment of the present disclosure 1~45.47N@N-rGO-650、Co5.47N@N-rGO-700、Co5.47N@N-
rGO-750、Co5.47The cyclic voltammetry curve (CV) of N@N-rGO-800；
Fig. 8 is Co prepared by the embodiment of the present disclosure 1~45.47N@N-rGO-650、Co5.47N@N-rGO-700、Co5.47N@N-
rGO-750、Co5.47The ORR-OER polarization curve of N@N-rGO-800；
Fig. 9 is Co prepared by the embodiment of the present disclosure 35.47N N-rGO-750 catalyst following in liquid zinc-air battery
Ring charging and discharging curve；
Figure 10 is Co prepared by the embodiment of the present disclosure 1~45.47N@N-rGO-650、Co5.47N@N-rGO-700、Co5.47N@
N-rGO-750、Co5.47The HER polarization curve of N@N-rGO-800 and Pt/C.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the disclosure.Unless another
It indicates, all technical and scientific terms used herein has usual with disclosure person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
The multi-functional elctro-catalyst of ORR, HER and OER generally can not be used as simultaneously in view of existing noble metal-based catalysts, this
It is open to propose a kind of cobalt nitride and be embedded in porous nitrogen-doped graphene material and preparation method and application.
A kind of exemplary embodiment of the disclosure provides a kind of porous nitrogen-doped graphene material of cobalt nitride insertion, packet
Include nitrogen-doped graphene and Co5.47There is the cavernous structure of vermiform trace on N nano particle, the nitrogen-doped graphene surface,
Co5.47N nano particle is embedded in the end of the cavernous structure of vermiform trace.
Co in the material that the disclosure provides5.47N nano particle is embedded in the end of the cavernous structure of vermiform trace, can be with
Promote the quick interface electronics transfer and ion diffusion of respective reaction, while the poly- of nitridation cobalt nano-particle can be effectively inhibited
Collection and crushing, so that the material of the disclosure shows effective multi-functional catalysis to ORR, HER and OER in alkaline solution
Activity.
In one or more embodiments of the embodiment, graphene is redox graphene.
The another embodiment of the disclosure provides the preparation that a kind of cobalt nitride is embedded in porous nitrogen-doped graphene material
Method sequentially adds the uniformly mixed acquisition suspension of cobalt acetate, tannic acid into the dispersion liquid of graphene oxide, will be in suspension
Solid material separate after, be heated to being pyrolyzed not less than 600 DEG C under nitrogen and ammonia gas mixture atmosphere.
Tannic acid is there are benzene ring structure in the disclosure, can with the electrostatic interaction of graphene oxide pi-pi accumulation so that
Tannic acid can be stable combination on graphene oxide, while in tannic acid two adjacent phenol oxygen molecules to Co2+Ion
Empty d track provides lone pair electrons, to form five yuan of stable chelate rings, and then can be by tannic acid by Co2+Ion dispersion
To surface of graphene oxide.Secondly, being found through experiments that only cobalt acetate could be by the above method on nitrogen-doped graphene
It is embedded in Co5.47N, and other cobalt salts, such as cobalt chloride, cobalt nitrate, cobaltous sulfate etc., can not be embedded on nitrogen-doped graphene
Co5.47N.The preparation method of third, the disclosure can make the Co to be formed5.47N nanoparticle is on redox graphene surface
Thermal etching movement will lead to the formation vermiform hole in nitridation process, and it is living to enhance electro-catalysis that this will generate more surface defects
Property.
Pyrolysis realizes the synchronous reduction of GO and in NH in the disclosure3In the presence of Co is formed in situ5.47N nano particle.
In one or more embodiments of the embodiment, it is equal that dispersion is added into graphene oxide dispersion in cobalt acetate
It is even, tannic acid is then added and is uniformly mixed acquisition suspension, after the solid material separation in suspension, washs drying, then
It is heated to being pyrolyzed not less than 600 DEG C under nitrogen and ammonia gas mixture atmosphere.
In one or more embodiments of the embodiment, graphene oxide, cobalt acetate, tannic acid additional proportion be 55
~65:0.001~0.003:0.7~0.8, mg:mol:g.
In one or more embodiments of the embodiment, the volume ratio of nitrogen and ammonia is 2.5~3.5:1.
In one or more embodiments of the embodiment, the temperature of pyrolysis is 650~800 DEG C.When pyrolysis temperature is 740
At~760 DEG C, the performance for preparing material is more preferable.
In one or more embodiments of the embodiment, the temperature of pyrolysis is 0.5~5h.
The graphene oxide of the disclosure is the Hummers method preparation by natural graphite flakes by improvement.
The third of the disclosure is embedded in porous nitrogen-doped graphene material embodiment there is provided a kind of above-mentioned cobalt nitride and exists
Application in metal-air battery field and/or electrolysis water.
Embodiment there is provided a kind of electrode materials, including above-mentioned cobalt nitride to be embedded in porous nitrogen and mix for the 4th kind of the disclosure
Miscellaneous grapheme material.
Embodiment there is provided a kind of zinc-air batterys for the 5th kind of the disclosure, are embedded in porous nitrogen with above-mentioned cobalt nitride and mix
Miscellaneous grapheme material is as air cathode catalyst.
In one or more embodiments of the embodiment, cobalt nitride is embedded in porous nitrogen-doped graphene using adhesive
Material is coated on carbon paper, is dried and is prepared air cathode.
In one or more embodiments of the embodiment, the zinc-air battery is water system zinc-air battery or solid zinc
Air cell.
For the 6th kind of the disclosure embodiment there is provided a kind of elctro-catalyst, active constituent is that the insertion of above-mentioned cobalt nitride is more
Hole nitrogen-doped graphene material.
Embodiment there is provided a kind of methods of electrolysis water for the 7th kind of the disclosure, are embedded in porous nitrogen with above-mentioned cobalt nitride
Doped graphene material uses the power supply of water system zinc-air battery by water decomposition for hydrogen and oxygen as elctro-catalyst.
In one or more embodiments of the embodiment, the battery is zinc-air battery.
When carrying out water decomposition in order to which more convenient test, in the disclosure, the zinc-air battery used is the disclosure
The zinc-air battery of offer.
In order to enable those skilled in the art can clearly understand the technical solution of the disclosure, below with reference to tool
The technical solution of the disclosure is described in detail in the embodiment of body.
The graphene oxide (GO) used in following embodiment passes through the Hummers method system of improvement by natural graphite flakes
It is standby.
Embodiment 1
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, 2mmol is then added under vigorous stirring
(0.4982g)Co(OAc)2·4H2O.Then, tannic acid (0.75g) is dissolved in 10mL deionized water and above-mentioned mixing is added
In solution.Obtained suspension is centrifuged and is washed, and is subsequently dried 12 hours with liquid nitrogen fast freezing.By gained sample loading tube
In formula furnace and in N2: NH3Than being heated to 650 DEG C in the atmosphere for 3:1 with the rate of heat addition of 10 DEG C/min, it is pyrolyzed 1 hour, obtains
Sample is denoted as Co5.47N@N-rGO-650。
Embodiment 2
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, 2mmol is then added under vigorous stirring
(0.4982g)Co(OAc)2·4H2O.Then, tannic acid (0.75g) is dissolved in 10mL deionized water and above-mentioned mixing is added
In solution.Obtained suspension is centrifuged and is washed, and is subsequently dried 12 hours with liquid nitrogen fast freezing.By gained sample loading tube
In formula furnace and in N2: NH3Than being heated to 700 DEG C in the atmosphere for 3:1 with the rate of heat addition of 10 DEG C/min, it is pyrolyzed 1 hour, obtains
Sample is denoted as Co5.47N@N-rGO-700。
Embodiment 3
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, then it is added under vigorous stirring
0.4982gCo(OAc)2·4H2O.Then, tannic acid (0.75g) is dissolved in 10mL deionized water and that above-mentioned mixing is added is molten
In liquid.Obtained suspension is centrifuged and is washed, and is subsequently dried 12 hours with liquid nitrogen fast freezing.Gained sample is packed into tubular type
In furnace and in N2: NH3Than being heated to 750 DEG C in the atmosphere for 3:1 with the rate of heat addition of 10 DEG C/min, it is pyrolyzed 1 hour, obtains sample
Product are denoted as Co5.47N@N-rGO-750。
Embodiment 4
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, 2mmol is then added under vigorous stirring
(0.4982g)Co(OAc)2·4H2O.Then, tannic acid (0.75g) is dissolved in 10mL deionized water and above-mentioned mixing is added
In solution.Obtained suspension is centrifuged and is washed, and is subsequently dried 12 hours with liquid nitrogen fast freezing.By gained sample loading tube
In formula furnace and in N2: NH3Than being heated to 800 DEG C in the atmosphere for 3:1 with the rate of heat addition of 10 DEG C/min, it is pyrolyzed 1 hour, obtains
Sample is denoted as Co5.47N@N-rGO-800。
Embodiment 5
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, 2mmol is then added under vigorous stirring
(0.4982g)Co(OAc)2·4H2O.Then, tannic acid (0.75g) is dissolved in 10mL deionized water and above-mentioned mixing is added
In solution.Obtained suspension is centrifuged and is washed, and is subsequently dried 12 hours with liquid nitrogen fast freezing.By gained sample loading tube
In formula furnace and in N2: NH3Than being heated to 750 DEG C in the atmosphere for 3:1 with the rate of heat addition of 10 DEG C/min, it is pyrolyzed 2 hours, obtains
Sample is denoted as Co5.47N@N-rGO-750-2h。
Embodiment 6
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, 2mmol is then added under vigorous stirring
(0.4982g)Co(OAc)2·4H2O.Then, tannic acid (0.75g) is dissolved in 10mL deionized water and above-mentioned mixing is added
In solution.Obtained suspension is centrifuged and is washed, and is subsequently dried 12 hours with liquid nitrogen fast freezing.By gained sample loading tube
In formula furnace and in N2: NH3Than being heated to 750 DEG C in the atmosphere for 3:1 with the rate of heat addition of 10 DEG C/min, it is pyrolyzed 3 hours, obtains
Sample is denoted as Co5.47N@N-rGO-750-3h。
Embodiment 7
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, 2mmol is then added under vigorous stirring
(0.4982g)Co(OAc)2·4H2O.Obtained suspension is centrifuged and is washed, and is subsequently dried 12 hours with liquid nitrogen fast freezing.
Gained sample is fitted into tube furnace and in N2: NH3Than being heated to 750 in the atmosphere for 3:1 with the rate of heat addition of 10 DEG C/min
DEG C, it is pyrolyzed 1 hour, obtains sample, be denoted as Co@N-rGO-750.
Embodiment 8
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, 2mmol is then added under vigorous stirring
(0.4759g)CoCl2·6H2O.Then, tannic acid (0.75g) is dissolved in 10mL deionized water and that above-mentioned mixing is added is molten
In liquid.It can not be reacted.
Embodiment 9
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, 2mmolCo is then added under vigorous stirring
(NO3)2·6H2O(0.5821g).Then, tannic acid (0.75g) is dissolved in 10mL deionized water and that above-mentioned mixing is added is molten
In liquid.It can not be reacted.
Embodiment 10
By GO dispersion liquid (the 1.5mg mL of 40mL-1) ultrasonic treatment 20 minutes, then it is added under vigorous stirring
2mmolCoSO4·7H2O(0.5622g).Then, tannic acid (0.75g) is dissolved in 10mL deionized water and is added above-mentioned mixed
It closes in solution.It can not be reacted.
The specimen material of preparation in the above various embodiments is characterized
Structural characterization
Scanning electron microscope (SEM) is carried out by Gemini-SEM-300, Carl Zeiss Microscopy GmbH,
Transmission electron microscope (TEM) carries out on JEOL 2100PLUS.X is carried out by using X'Pert3 powder x-ray diffraction
X ray diffraction (XRD).High resolution transmission electron microscope (HRTEM) carries out on the FEI-TF20 of scientific compass.It uses up
Electron spectrometer (ESCALAB 250) carries out x-ray photoelectron spectroscopy (XPS).Raman spectrum is used on LabRAM HR800
The excitation laser of 532nm carries out.N is measured at 77K using BJ Builder Kubo-X1000 instrument2Adsorption isotherm.
Electrochemical Characterization
By using the CHI 760E electrochemical workstation (CH Instrument, Shanghai) with three-electrode system
Carry out electro-chemical test.The glass carbon rotating ring disk electrode (r.r.d.e) (RRDE) that prepared catalyst will be coated with is used as working electrode, and Ag/
AgCl electrode and graphite rod (or Pt piece) are used separately as reference electrode and to electrode.Relative to all electricity of Ag/AgCl electrode measurement
Position, and reversible hydrogen electrode is calibrated to according to following equation: ERHE=EAg/AgCl+0.197+0.0591×pH.In order to prepare catalyst
Sample liquid, by the sample of each embodiment preparation of 5mg and 50 μ LNafion (5wt%) in 1mL ethanol solution (+250 μ L of 750 μ L water
Dehydrated alcohol) under ultrasonic treatment be blended to obtain homogeneous catalyst sample liquid.Then, 12 μ L catalyst sample drops are arrived
In glassy carbon electrode surface and it is dried at room temperature for.In order to compare, identical program preparation Pt/C (20wt%, ETEK) electricity is used
Pole.Cyclic voltammetry is measured in N2Or O2In the 0.1M KOH electrolyte of saturation with -1.0V to 0.2V (relative to Ag/AgCl) with
10mV s-1Sweep speed carry out.The LSV curve negotiating of oxygen reduction reaction (ORR) is using RDE in O2In the 0.1M KOH of saturation
With 5mV s-1Sweep speed carry out, catalyst loadings be 0.24mg cm-2.Oxygen evolution reacts (OER) and evolving hydrogen reaction
(HER) measurement is respectively in O2、N2With 5mV s in the 1.0M KOH of saturation-1Sweep speed carry out, catalyst loadings are
0.5mg cm-2.Carbon paper area used is (1 × 1 centimetre).
The assembling of zinc-air battery
Pass through catalyst ink (the 5mg ml that will be prepared-1) polytetrafluoroethylene (PTFE) (PTFE) is used to be coated in carbon paper as adhesive
On, and dry 2 hours at 80 DEG C prepare air electrode, catalyst loadings are 0.75mg cm-2。
Water system zinc-air battery: liquid electrolyte is housed, air electrode and zinc metal sheet are respectively as cathode in electrochemical cell
And anode, liquid electrolyte are 6M potassium hydroxide and 0.2M zinc acetate.
Solid-state zinc-air battery: 6.3g KOH is mixed in 9mL water with 0.20g ZnO, and acquired solution is referred to as molten
Liquid A, by 0.15g N, N'- methylene-bisacrylamide (MBA) is added 0.95mL acrylic acid and prepares solution B, then, by solution A
It together with being slowly mixed together with solution B and is kept stirring 5 minutes, then, 120 μ LK is added2S2O8Polypropylene is obtained to cause polymerization
Sour (PAA) gel solid electrolyte.The air electrode prepared and zinc foil and a piece of polymer dielectric are assembled into Sanming City
Structure is controlled, and is sealed with acrylic adhesive tape.
Characterization result
Pass through the form and structure of SEM and tem observation all samples.As shown in Figure 1a, Co5.47The SEM of N@N-rGO-750
Image, which shows to have, is permitted porous two dimension rGO piece, Co5.47N nano particle is uniformly dispersed on it.The SEM image of amplification is aobvious
Show that nano particle is evenly dispersed on the surface of rGO, and on the surface it can be seen that many vermiform holes.In particular,
The TEM image of amplification shows that the vermiform trace on rGO piece surface forms nano particle (Fig. 1 b) in end of trace.Co5.47N receives
Thermal etching movement of the rice corpuscles on the surface rGO will lead to the formation vermiform hole in nitridation process, this will generate more tables
Planar defect is to enhance electro catalytic activity.Under identical pyrolysis temperature, Co5.47The partial size of N@N-rGO-750 is much smaller than and does not add
The partial size of the Co@N-rGO-750 prepared when TA.These results indicate that the size of TA not only adjustable cobalt compound, may be used also
To ensure that complete inversion of phases is Co in pyrolytic process5.47N。Co5.47The presence of graphite linings outside N nanoparticle shows
Co5.47It closely interacts between the graphite carbon substrate of N and N doping, and further improves the mechanical stability of catalyst.Than
Compared with the sample obtained under different pyrolysis temperatures, many wrinkles and seldom hole (figure are observed on the surface rGO at 650 DEG C
2a-c), this is similar to naked rGO.As pyrolysis temperature is increased to 700 DEG C, the particle size on the surface rGO becomes larger, and by
In the thermal etching of nano particle, some vermiform channels (Fig. 2 d-f) is observed.750 DEG C at a temperature of, it is evident that Ke Yiqing
Observe to Chu the structure (Fig. 1 a and 1b) in vermiform channel.However, being formed has macropore and burning when temperature reaches 800 DEG C
Tie the rGO piece (Fig. 2 g-i) of particle.The result shows that nano particle moves together aggregation at high temperature, simultaneously because in metal
The thermal decomposition of carbon in the presence of catalyst, rGO sheet material will be etched.It further proves, as annealing time increased to 3 from 2 hours
Hour, rGO piece is gradually etched and disappears (Figure 4 and 5).Under longer calcination time, formed due to heat accumulation have compared with
Large-sized Co5.47N nano particle (Fig. 5).
Powder XRD analysis is carried out to characterize prepared Co5.47The crystal structure of N@N-rGO.As shown in figure 3, being located at
43.7,50.8 the diffraction maximum with 74.9 ° corresponds to Co5.47(111), (200) and (220) plane of N, it was confirmed that Co5.47The shape of N
It is considered as (002) graphite plane of N-rGO at the wide diffraction maximum at .26 °.As previously mentioned, Co5.47The crystal structure of N phase is
Some N atoms have been lacked in the octahedral interstice of Co metal lattice, and have formed corresponding vacancy, this not only ensure that Co5.47N's
Metallic character, but also more active sites are enhanced by the generation in nitrogen vacancy.When calcination temperature is increased to from 650 DEG C
At 800 DEG C, the diffraction peak intensity of graphitic carbon is gradually decreased, this is because rGO piece is gradually etched as temperature increases.
In order to study Co5.47The ORR catalytic activity of N@N-rGO sample, in N2And O2It is carried out in the 0.1M KOH solution of saturation
Cyclic voltammetric (CV) test.As shown in fig. 7, in N2Any reduction peak is not observed in saturation electrolyte.On the contrary, working as electrolyte
By O2When saturation, occurs apparent reduction peak near 0.94V, this is attributed to the reduction of oxygen.The hydrogen reduction peak observed with
Pyrolysis temperature be increased to 750 DEG C from 650 DEG C and shift to the current potential of corrigendum, but when temperature being further increased to 800 DEG C
Activity slightly weakens.It is worth noting that, Co5.47The oxygen reduction current potential of N@N-rGO-750 electrode is catalyzed better than business Pt/C
Agent (Pt/XC-72 20wt%) shows that its ORR electro catalytic activity is more superior.
Total polarization curve of ORR and OER is as shown in figure 8, Co5.47N@N-rGO-750 has best double-function catalyzing activity,
Δ E=0.77V (Δ E=EOER-EORR, wherein EOERFor 10mA cm-2Current density under current potential, EORRFor half wave potential).So
And Co5.47N@N-rGO-650, Co5.47N@N-rGO-700,Co5.47The Δ E of N@N-rGO-800 and Pt/C are respectively 0.88,
And 0.97V 0.83,0.91.Therefore, Co5.47N@N-rGO-750 has the application of superior double-function catalyzing zinc-air battery
Potentiality.
In view of the difunctional activity of its ORR and OER, with Co5.47N@N-rGO-750 catalyst is air-electrode catalyst
Agent assembles the chargeable zinc-air battery of water system using 6M potassium hydroxide and 0.2M zinc acetate as electrolyte, and Fig. 9 shows zinc-
The cycle charge discharge electrical property of air cell, it can be found that Co5.47N@N-rGO-750 electrode can continuously recycle in 330 hours
2000 circulations, and only observe slight potential change, show Co5.47N@N-rGO-750 electrode has good follow
Ring stability.
The disclosure uses Co5.47N@N-rGO-750 elctro-catalyst is as the further assembling solid zinc of air cathode-air electricity
Pond, wherein zinc foil is as anode.For adapt to Portable flexible device development trend, using polyacrylic acid (PAA) gel electrolyte
Matter assembles solid zinc-air battery.After tested, Co5.47The charging/discharging voltage difference of N@N-rGO-750 electrode is less than Pt/C-RuO2
Electrode illustrates Co5.47N@N-rGO-750 elctro-catalyst it is more efficient.In addition, and Pt/C-RuO2(24.7mW cm-2) compare,
Co5.47The power density of N@N-rGO-750 is higher, is 54.6mW cm-2.It is worth noting that, discharge current density is 10mA
cm-2When specific capacity be about 518mAh gzn -1(by the mass normalisation of consumption zinc), is slightly larger than Pt/C-RuO2 (506mAh gzn -1) specific capacity, illustrate that its discharge-rate is had excellent performance.Co5.47The flexibility and stability test of N@N-rGO-750 is close in electric current
Degree is 1mA cm-2Place is also assessed, it can be found that Co5.47N@N-rGO-750 electrode charge and discharge voltage almost without decaying,
Illustrate that solid zinc-air battery has good flexible application potentiality.Co5.47N@N-rGO-750 air cathode has long-term circulation
Stability and reversibility, 40h or more have no apparent potential decay, illustrate there is good invertibity.In addition, Co5.47N@N-
For rGO-750 in the 240th charge and discharge cycles, voltage efficiency can still keep 56%, further illustrate that its stability is preferable.
Co5.47The HER catalytic activity of N@N-rGO catalyst and business Pt/C are as shown in Figure 10.Co5.47N@N-rGO-750 electricity
Pole shows fairly good HER electro catalytic activity, has the take-off potential (- 0.1V vs.RHE) of corrigendum, current density reaches
10mA cm-2Corresponding overpotential is only 0.19V, is better than Co5.47N@N-rGO-650 (0.26V), Co5.47@N-rGO-700
(0.22V), Co5.47N@N-rGO-800(0.23V).These are the result shows that Co5.47N@N-rGO-750 electrode have excellent ORR,
The multi-functional electro catalytic activity of OER and HER.
Conclusion
The disclosure has developed a kind of green and easy technique, is dispersing agent and chelating agent in rGO piece using tannic acid
Upper fabricated in situ nitrogenizes cobalt nano-particle.Co5.47Being formed in situ for N nanoparticle causes on the surface rGO with warm-up movement etching
Form vermiform channel and hole.Have benefited from Co5.47The intrinsic high conductivity of N nano particle and the association of nitrogen atom doping graphene
Same advantage, Co5.47N@N-rGO-750 has outstanding electro catalytic activity to ORR, HER and OER, can assemble chargeable zinc
Air cell and overall moisture solution device.Particularly, using Co5.47N@N-rGO-750 is empty as the chargeable zinc of air cathode
Gas exhibits more than the excellent cycling stability of 330h.Solid-state zinc-air battery also shows good rechargeable performance (about
40h).In addition, being shown by the water dissociation device that zinc-air battery drives good by using prepared elctro-catalyst
The rate of gas production.
The foregoing is merely preferred embodiment of the present disclosure, are not limited to the disclosure, for the skill of this field
For art personnel, the disclosure can have various modifications and variations.It is all within the spirit and principle of the disclosure, it is made any to repair
Change, equivalent replacement, improvement etc., should be included within the protection scope of the disclosure.
Claims (10)
1. a kind of cobalt nitride is embedded in porous nitrogen-doped graphene material, characterized in that including nitrogen-doped graphene and Co5.47N nanometers
There are the cavernous structure of vermiform trace, Co in particle, the nitrogen-doped graphene surface5.47N nano particle is embedded in vermiform mark
The end of the cavernous structure of line.
2. cobalt nitride as described in claim 1 is embedded in porous nitrogen-doped graphene material, characterized in that graphene is oxygen reduction
Graphite alkene.
3. the preparation method that a kind of cobalt nitride is embedded in porous nitrogen-doped graphene material, characterized in that point of graphene oxide
The uniformly mixed acquisition suspension of cobalt acetate, tannic acid is sequentially added in dispersion liquid, after the solid material in suspension is separated,
It is heated to being pyrolyzed not less than 600 DEG C under nitrogen and ammonia gas mixture atmosphere.
4. the preparation method that cobalt nitride as claimed in claim 3 is embedded in porous nitrogen-doped graphene material, characterized in that by vinegar
Sour cobalt is added to be uniformly dispersed into graphene oxide dispersion, and tannic acid is then added and is uniformly mixed acquisition suspension, will suspend
After solid material separation in liquid, drying is washed, not less than 600 DEG C progress are then heated under nitrogen and ammonia gas mixture atmosphere
Pyrolysis.
5. the preparation method that cobalt nitride as claimed in claim 4 is embedded in porous nitrogen-doped graphene material, characterized in that oxidation
Graphene, cobalt acetate, tannic acid additional proportion be 55~65:0.001~0.003:0.7~0.8, mg:mol:g；
Or, the volume ratio of nitrogen and ammonia is 2.5~3.5:1；
Or, the temperature of pyrolysis is 650~800 DEG C；Preferably, 740~760 DEG C；
Or, the temperature of pyrolysis is 0.5~5h.
6. a kind of cobalt nitride of any of claims 1 or 2 is embedded in porous nitrogen-doped graphene material or claim 3~5 is any
The cobalt nitride that the preparation method obtains is embedded in porous nitrogen-doped graphene material in metal-air battery field and/or electrolysis
Application in water.
7. a kind of electrode material, characterized in that be embedded in porous nitrogen-doped graphene including cobalt nitride of any of claims 1 or 2
The cobalt nitride that material or any preparation method of claim 3~5 obtain is embedded in porous nitrogen-doped graphene material.
8. a kind of zinc-air battery, characterized in that be embedded in porous nitrogen-doped graphene with cobalt nitride of any of claims 1 or 2
The cobalt nitride that material or any preparation method of claim 3~5 obtain is embedded in porous nitrogen-doped graphene material conduct
Air cathode；
Preferably, cobalt nitride is embedded in porous nitrogen-doped graphene material coated on carbon paper using adhesive, system is dried
It is standby to obtain air cathode；
Preferably, the zinc-air battery is liquid zinc-air battery or solid-state zinc-air battery.
9. a kind of elctro-catalyst, characterized in that active constituent is that cobalt nitride of any of claims 1 or 2 is embedded in porous N doping
The cobalt nitride that grapheme material or any preparation method of claim 3~5 obtain is embedded in porous nitrogen-doped graphene material
Material.
10. a kind of method of electrolysis water, characterized in that be embedded in porous N doping graphite with cobalt nitride of any of claims 1 or 2
The cobalt nitride that alkene material or any preparation method of claim 3~5 obtain is embedded in porous nitrogen-doped graphene material and makees
For elctro-catalyst, use battery by water decomposition for hydrogen and oxygen；
Preferably, the battery is zinc-air battery.
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