CN106887576A - Carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of a kind of cobalt and its preparation method and application - Google Patents
Carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of a kind of cobalt and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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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
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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
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- 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
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, the composite is with the nitrogen co-doped nitrogen carbon material of cobalt as carrier；The surface in situ load nickel oxide iron nano-particle of the nitrogen co-doped carbon material of the cobalt.The method that the present invention protects zeolite imidazole ester frame structure material presoma using silica; obtain high dispersive carbon-based nano granular materials; again by nickel-ferric spinel growth in situ on carbon material, calcining obtains the carrier loaded nanoscale nickel oxide iron composite material of the nitrogen co-doped nitrogen carbon material of cobalt.The carrier loaded nanoscale nickel oxide iron composite material of the nitrogen co-doped nitrogen carbon material of cobalt of the invention not only shows excellent activity in oxygen catalytic oxidation reduction reaction, and can be used as efficient zinc-air battery negative material.
Description
Technical field
The present invention relates to technical field of new energies.It is negative more particularly, to a kind of nitrogen co-doped nitrogen carbon material carrier of cobalt
Nano silicon nitride ferronickel composite of load and its preparation method and application.
Background technology
Zinc-air battery, due to cheap, environmental protection, specific energy density (1084Wh kg high-1), it is expected to turn into a new generation
The energy.Hinder at present its further it is wide variety of be, negative material oxygen catalytic oxidation (OER) used by zinc-air battery and and also
The efficiency of original reaction (ORR) is low.Respectively ORR and OER activity highest catalyst, however it is expensive, and reserves are rare, limitation
It is used in batch.Although researcher has found that some non-noble metallic materials can be used instead of noble metal, such as the carbon of N doping
The OER activity that the ORR activity of material alreadys exceed Pt, transition metal oxide/hydroxide/nitride/phosphide etc. has surpassed
More Ru/Ir.Can be while the bifunctional catalyst of efficient catalytic OER and ORR but still lack.
Nitridation ferronickel, because of its good conductivity, and is easy to form NiOOH on surface, in oxygen catalytic oxidation reaction (OER) tool
There is activity very high.But it is in building-up process, it is easy to reunite, it is unfavorable for that avtive spot fully exposes.
Therefore, the present invention proposes a kind of carrier loaded nanoscale nitridation ferronickel composite wood of the nitrogen co-doped nitrogen carbon material of cobalt
Material, makes full use of the synergy of nitridation ferronickel and the nitrogen co-doped carbon material of cobalt, obtains new, efficient bifunctional material, urges
Change dioxygen oxidation reduction reaction, and used as zinc-air battery negative material.
The content of the invention
It is an object of the present invention to provide a kind of carrier loaded nano silicon nitride nickel of the nitrogen co-doped nitrogen carbon material of cobalt
Iron composite material.
It is another object of the present invention to provide a kind of carrier loaded nano silicon nitride of the nitrogen co-doped nitrogen carbon material of cobalt
The preparation method of ferronickel composite.The present invention protects the side of zeolite imidazole ester frame structure material presoma using silica
Method, obtains high dispersive carbon-based nano granular materials, then by nickel-ferric spinel growth in situ on carbon material, calcining obtains cobalt nitrogen and is total to
The carrier loaded nanoscale nickel oxide iron composite material of the nitrogen carbon material of doping.
Third object of the present invention is to provide a kind of nitrogen co-doped nitrogen carbon material of cobalt carrier loaded nano silicon nitride
The application of ferronickel composite.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, the composite with
The nitrogen co-doped nitrogen carbon material of cobalt is carrier；The surface in situ load nitridation ferronickel nanometer of the nitrogen co-doped nitrogen carbon material of the cobalt
Particle.Present invention discover that the good conductivity of nitridation ferronickel, easily forms NiOOH on surface, oxygen catalytic oxidation reacts (OER), but
It is it in building-up process, it is easy to reunite, be unfavorable for that avtive spot fully exposes.Therefore the present invention is further to improve its OER
Reactivity, using the nitrogen co-doped nitrogen carbon material of cobalt as carrier.Present invention discover that the nitrogen co-doped carbon material of cobalt have it is excellent
Different electric conductivity, specific surface area high dispersibles nitridation ferronickel, fully exposes avtive spot, so as to promote OER reactivities.
Meanwhile, the nitrogen co-doped carbon material sheet of cobalt also shows that activity very high in redox reactions (ORR).Present invention warp
Cross ammonia calcining and obtain the nitrogen co-doped nitrogen carbon material carrier of cobalt, the increase of nitrogen on carbon skeleton does not change its ORR special
Property.
Preferably, the size of the nickel oxide iron nano-particle is 10~200nm；Further, it is of the invention some
In specific embodiment, for example, the size of the nickel oxide iron nano-particle be 10~100nm, 10~90nm, 10~80nm,
10~70nm, 10~60nm, 10~50nm, 10~40nm, 10~30nm, 10~20nm, 10~15nm etc.；It is highly preferred that institute
It is 20~90nm, 30~80nm, 40~70nm, 50~60nm etc. to state the size of nickel oxide iron nano-particle；It is highly preferred that described
The size of nickel oxide iron nano-particle is 20~80nm, 20~70nm, 20~60nm, 20~50nm, 20~40nm, 20~30nm
Deng；It is highly preferred that the size of the nickel oxide iron nano-particle is 30~70nm, 30~60nm, 30~50nm, 30~40nm
Deng；It is highly preferred that the size of the nickel oxide iron nano-particle is 40~60nm, 40~50nm etc..Ferronickel is nitrogenized in the present invention
Size be raw material proportioning, preparation process and technological parameter cooperate, coefficient result.It is a discovery of the invention that by adjusting
Whole raw material proportioning, preparation process and technological parameter, the size of the nickel oxide iron nano-particle for obtaining are smaller, and final cobalt is nitrogen co-doped
The carrier loaded nano silicon nitride ferronickel composite of nitrogen carbon material activity it is higher, be in the size of nickel oxide iron nano-particle
During 10~20nm, the OER activity of the composite for obtaining is optimal.
Preferably, the mass percent of nickel oxide iron nano-particle is 33.3~66.7wt% in the composite；More
Preferably, the mass percent of nickel oxide iron nano-particle is 50wt% in the composite；Present invention discover that in the quality
OER the and ORR activity of the composite obtained under percentage is optimal.
To reach above-mentioned second purpose, the present invention uses following technical proposals：
A kind of preparation method of the carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, including
Following steps：
1) the carrier loaded nanometer nickel-ferric spinel composite of the nitrogen co-doped carbon material of cobalt i.e. Co, N-CNF is prepared, i.e.,
NiFe-LDH/Co,N-CNF
By the nitrogen co-doped carbon material of cobalt, i.e. Co, N-CNF, in after organic solvent for ultrasonic dispersion, addition contains Ni
(NO3)2·6H2O, Fe (NO3)3·9H2The mixed solution of O and urea, NiFe- is dried to obtain after stirring reaction after washing, centrifugation
LDH/Co,N-CNF。
2) the carrier loaded nano silicon nitride ferronickel composite of cobalt nitrogen co-doped nitrogen carbon material i.e. Co, N-NCNF is prepared,
That is Ni3FeN/Co,N-NCNF
By step 1) in the NiFe-LDH/Co that obtains, N-CNF obtains Ni in ammonia atmosphere after calcining3FeN/Co,N-
NCNF.Hydroxide is converted into nitride by the present invention by the use of ammonia as nitrogen source, and by Co, N-CNF is converted into Co, N-
NCNF。
Preferably, step 1) described in cobalt nitrogen co-doped carbon material zeolite imidazole ester skeleton knot is protected using silica
It is prepared by the method for structure material precursor；Present invention discover that being solved using the nitrogen co-doped carbon material of the cobalt that the method is prepared
The agglomeration traits that presoma faces in high-temperature calcination, so as to obtain the porous nano carbon nano-particle of high degree of dispersion, under being
One step growth in situ hydrotalcite provides the specific surface area in more load sites；The preparation method is document L.Shang,
H.Yu,X.Huang,T.Bian,R.Shi,Y.Zhao,G.I.N.Waterhouse,L.Z.Wu,C.H.Tung,T.Zhang,
Well-Dispersed ZIF-Derived Co,N-Co-doped Carbon Nanoframes through
Mesoporous-Silica-Protected Calcination as Efficient Oxygen Reduction
Method described in Electrocatalysts Adv.Mater.2016,28,1668.
Preferably, step 1) described in the nitrogen co-doped carbon material of cobalt the mol ratio of Co, N and C be 0.5~5:1~10:
90.It is highly preferred that step 1) described in the nitrogen co-doped carbon material of cobalt the mol ratio of Co, N and C be 2:5:90, present invention hair
It is existing, 2:5:Under 90 mol ratios, the nitrogen co-doped carbon material ORR activity highests of cobalt.
Preferably, step 1) described in organic solvent be that to be suitable to the nitrogen co-doped carbon material of cobalt fully decentralized any organic
Solvent, it is highly preferred that the organic solvent is dimethyl pyrrolidone.
Preferably, step 1) described in the addition of the nitrogen co-doped carbon material of cobalt be that every mL organic solvents add 0.625
The nitrogen co-doped carbon material of the cobalt of~2.5mg；It is highly preferred that step 1) described in the addition of the nitrogen co-doped carbon material of cobalt be
The nitrogen co-doped carbon material of the cobalt of 1.25~1.5mg is added per mL organic solvents.
Preferably, step 1) described in ultrasonic disperse time be 0.5~1h.
Preferably, step 1) described in Ni (NO in mixed solution3)2·6H2O、Fe(NO3)3·9H2O and urea mole
Than being 1.25~1.3：0.42：150, the mixed solution is 2.5~3 with the volume ratio of organic solvent：1.Present invention discover that mixed
Close presoma Ni (NO in solution3)2·6H2O and Fe (NO3)3·9H2The mol ratio of O is too high or too low, subsequently will be unable to obtain
Ni3FeN particles, and Ni (NO in mixed solution3)2·6H2O and urea mol ratio are too high or too low, then cannot obtain small size
NiFe-LDH, cannot further obtain the Ni of small size3FeN particles.
Preferably, step 1) described in reaction temperature be 95~100 DEG C, the reaction time be 6~8h；
Preferably, step 1) described in wash the solvent including but not limited to second alcohol and water of use, the drying temperature is
50~60 DEG C；The drying time is 6~12h.
Preferably, step 2) described in calcining heat be 400~700 DEG C, the calcination time be 1~3h.
To reach above-mentioned 3rd purpose, the present invention uses following technical proposals：
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt is used as electro-catalysis oxygen
The application of the catalyst of redox reaction.Present invention discover that the carrier loaded nano silicon nitride nickel of the nitrogen co-doped nitrogen carbon material of cobalt
Iron composite material shows excellent activity in electro-catalysis oxygen redox reaction.
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt is used as zinc-air battery
The application of negative material.Present invention discover that the carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt can
Used as efficient zinc-air battery negative material.
As the nitrogen co-doped carbon material of the cobalt of carrier and it is carried on carbon material between nano silicon nitride ferronickel in the present invention
Cooperate, synergy, not only improve nitridation ferronickel building-up process be easy to reunite, avtive spot cannot be fully exposed
Problem, and the not nitrogen co-doped carbon material of influence cobalt redox reactions activity in itself, the composite tool for finally giving
There is excellent double function characteristic.
In addition, unless otherwise specified, any scope described in the present invention includes any number between end value and end value
Any subrange that any number between value and end value or end value is constituted.
Beneficial effects of the present invention are as follows：
(1) present invention is by nanometer nickel-ferric spinel growth in situ on the nitrogen co-doped nitrogen carbon material carrier material of cobalt
The nitridation ferronickel of small size is further generated at a lower temperature, there is provided important premise.
(2) present invention in be highly dispersed on the nitrogen co-doped nitrogen carbon material of cobalt and small size nitridation ferronickel, with rich
Rich avtive spot and good charge transfer, are that the carrier loaded nano silicon nitride ferronickel of the nitrogen co-doped nitrogen carbon material of cobalt is combined
Material shows the key of excellent activity in OER reactions.
(3) addition of high conductivity nitridation ferronickel and the calcining of ammonia do not influence the nitrogen co-doped nitrogen of cobalt in the present invention
The ORR of carbon material is active, and the carrier loaded nano silicon nitride ferronickel composite of the nitrogen carbon material for making cobalt nitrogen co-doped can be used as height
The zinc-air battery negative material of effect is used.
Brief description of the drawings
Specific embodiment of the invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows Ni in the embodiment of the present invention 13The powder X-ray diffractogram of FeN/Co, N-NCNF composite.
Fig. 2 shows Ni in the embodiment of the present invention 13The transmission electron microscope picture of FeN/Co, N-NCNF composite.
Fig. 3 a show Ni in the embodiment of the present invention 13FeN/Co, N-NCNF composite oxygen catalytic oxidation reactivity worth
Map of current.
Fig. 3 b show Ni in inventive embodiments 13The electricity of FeN/Co, N-NCNF composite catalytic oxygen reduction reaction performance
Flow graph.
Fig. 4 shows the map of current of zinc-air battery discharge and recharge in the embodiment of the present invention 1.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
In the description of the invention, unless otherwise indicated, " multiple " is meant that two or more；Term " on ",
The orientation or position relationship of the instruction such as D score, "left", "right", " interior ", " outward ", " front end ", " rear end ", " head ", " afterbody " are
Based on orientation shown in the drawings or position relationship, it is for only for ease of and describes the present invention and simplify to describe, rather than instruction or dark
Showing the device or element of meaning must have specific orientation, with specific azimuth configuration and operation therefore it is not intended that right
Limitation of the invention.
The nitrogen co-doped carbon material of cobalt, i.e. Co in the present invention, (mol ratio of Co, N, C is 2 to N-CNF:5:90), preparation side
Method uses document L.Shang, H.Yu, X.Huang, T.Bian, R.Shi, Y.Zhao, G.I.N.Waterhouse, L.Z.Wu,
C.H.Tung,T.Zhang,Well-Dispersed ZIF-Derived Co,N-Co-doped Carbon Nanoframes
through Mesoporous-Silica-Protected Calcination as Efficient Oxygen Reduction
Electrocatalysts Adv.Mater.2016, the method described in 28,1668, comprise the following steps that：
A) by the Co (NO of 10.8mmol3)2·6H2Zn (the NO of O and 54mmol3)2·6H2O is dissolved in 1000mL methyl alcohol and obtains
To solution A.
B) 270mmol methylimidazoles are dissolved in 800mL methyl alcohol and obtain solution B.
C) B solution is poured into solution A, 2h is stirred at room temperature after being stirred at room temperature, cleaned through methyl alcohol, centrifugation obtains zinc cobalt doped
Zeolite imidazole ester frame structure material.
D) by all Zn in undried step c), Co-ZIF is dissolved in 500mL water, sequentially adds 62.5mL concentration and is
25mg mL-1The CTAB aqueous solution, the 6mg mL that 35mL concentration is-1The NaOH aqueous solution, and after the TEOS of 7.5mL, stirring
30min, washs through ethanol, and centrifugation obtains the zeolite imidazole of the zinc cobalt doped of mesoporous silicon oxide cladding after 80 DEG C of oven dryings
Ester frame structure material is Zn, Co-ZIF@mSiO2。
E) by Zn in step d), Co-ZIF@mSiO2900 DEG C of calcining 2h, are cooled to room temperature, with dense in nitrogen atmosphere
After spending the HF solution immersion 10min for 10wt%, cleaned with water and ethanol, 60 DEG C of oven dryings are placed in after centrifugation.
Embodiment 1
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is as follows：
1) cobalt nitrogen co-doped carbon material Co, N-CNF carrier loaded nanometer nickel-ferric spinel composite NiFe-LDH/
The preparation of Co, N-CNF：
Take the Co of 25mg, the N-CNF (mol ratios of Co, N, C：2:5:90) ultrasonic disperse in 20mL dimethyl pyrrolidones
After 30 minutes, 50mL is added to contain 367.5mg Ni (NO3)2·6H2O,170mg Fe(NO3)3·9H2O and 9g urea it is water-soluble
Liquid, in after 100 DEG C of stirring reaction 6h, is cleaned with water and ethanol, 60 DEG C of oven dryings is placed in after centrifugation and obtains NiFe-LDH/Co,
N-CNF。
2) cobalt nitrogen co-doped nitrogen carbon material Co, N-NCNF carrier loaded nano silicon nitride ferronickel composite Ni3FeN/
The preparation of Co, N-NCNF：
By step 1) in the NiFe-LDH/Co that obtains, N-CNF calcines 2 hours for 400 DEG C in ammonia atmosphere, obtains
Ni3FeN/Co,N-NCNF。
The Ni of preparation3The powder X-ray diffractogram of FeN/Co, N-NCNF composite is as shown in figure 1, spreading out in figure
Penetrate peak and Ni3The standard diffraction peak of FeN and graphitized carbon coincide.The Ni of preparation3The transmission of FeN/Co, N-NCNF composite
Electromicroscopic photograph is as shown in Fig. 2 each granular size is the nitridation ferronickel nanometer of load 10-20nm in situ on the porous carrier of 70nm
Particle.
The Ni that will be prepared in the present embodiment3FeN/Co, N-NCNF are used for electro-catalysis dioxygen oxidation also as catalyst
Original reaction：By Ni3FeN/Co, N-NCNF composite are coated on electrochemistry glass-carbon electrode, anti-using three electrodes in alkali lye
Answer device, test electro-catalysis oxygen redox reaction in the solution, voltage with electric current change.As best shown in figures 3 a and 3b, OER
Some positions are crossed for 0.27V (with respect to reversible hydrogen electrode), ORR half wave potentials are 0.80V (with respect to reversible hydrogen electrode), illustrate the composite wood
Material has excellent dioxygen oxidation reduction reaction performance.
The Ni that will be prepared in the present embodiment3FeN/Co, N-NCNF are used for zinc-air battery as negative material：Will
Ni3FeN/Co, N-NCNF composite are coated on carbon paper, in alkali lye, using battery test system (indigo plant electricity CT 2001A),
The voltage of battery in atmosphere is tested with the change of electric current.The electric current collection of illustrative plates of battery charging and discharging is as shown in figure 4, in current density
It is 6mA cm-2When, can charge and discharge cycles be up to nearly 600h, and charge and discharge voltage difference be 0.8V.Illustrate to use Ni3FeN/Co,N-
NCNF composites have stabilization and energy efficiency well as the reversible zinc-air battery of negative material.
Embodiment 2~5
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 2) in calcining heat be respectively 450 DEG C, 550 DEG C, 600 DEG C, 700 DEG C.
Obtain Ni3FeN/Co, N-NCNF composite, size are as shown in table 1.
The Ni prepared under the different calcining heats of table 13The size of FeN/Co, N-NCNF composite
Learnt from table 1, be in the range of 400~700 DEG C, to be carried on the nitrogen co-doped nitrogen carbon material carrier of cobalt in calcining heat
On the size of nickel oxide iron nano-particle increase with the raising of calcining heat.Temperature cannot be obtained when too low or too high
Ni3FeN/Co, N-NCNF composite.
Comparative example 1~2
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 2) in calcining heat be respectively 300 DEG C, 800 DEG C when, cannot all obtain Ni3FeN/Co, N-NCNF composite wood
Material, is still NiFe-LDH/Co, N-NCNF after 300 DEG C of calcinings；800 DEG C, obtain Ni3Fe/Co, N-NCNF composite.
Embodiment 6~9
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in the consumption of nitrogen co-doped the carbon material Co, N-CNF of cobalt be respectively 12.5mg, 20mg, 35mg, 50mg.
Step 2) by step 1) in the NiFe-LDH/Co that obtains, N-CNF calcines 2 hours for 400 DEG C in ammonia atmosphere, obtains
To Ni3FeN/Co,N-NCNF。
Interpretation of result is as follows：
Step 1) NiFe-LDH/Co for preparing, N-CNF composites, as a result as shown in table 2.Step 2) it is prepared into
The Ni for arriving3FeN/Co, N-NCNF composite, as a result as shown in table 3
The NiFe-LDH/Co that the different ratios of raw materials of table 2 is obtained, the size of N-CNF composites
| Comparative example 3 | Embodiment 6 | Embodiment 7 | Embodiment 1 | Embodiment 8 | Embodiment 9 | Comparative example 4 | |
| The consumption (mg) of Co, N-CNF | 2 | 12.5 | 20 | 25 | 35 | 50 | 100 |
| Co, N-CNF size (nm) | 70 | 70 | 70 | 70 | 70 | 70 | 70 |
| NiFe-LDH sizes (nm) | 100-200 | 3~100 | 3~50 | 3~5 | 3~5 | 3~5 | 3~5 |
Learnt from table 2, the size of the nickel-ferric spinel nano particle on carrier is with the use of the nitrogen co-doped carbon material of cobalt
Amount increases and reduces, and to a certain extent, the nickel-ferric spinel particle size for obtaining no longer changes for consumption increase.Cobalt is nitrogen co-doped
The consumption of carbon material is too high, then the size constancy of NiFe-LDH；The consumption of the nitrogen co-doped carbon material of cobalt is too low, then NiFe-LDH
Free growth is 100-200nm.
The Ni that the different ratios of raw materials of table 3 is obtained3The size of FeN/Co, N-NCNF composite
Learnt from table 3, the size of the nickel oxide iron nano-particle on carrier is with the consumption of the nitrogen co-doped carbon material of cobalt
Increase and reduce, to a certain extent, the nickel oxide iron particle size for obtaining no longer changes for consumption increase.Because Ni3The size of FeN
Size with presoma NiFe-LDH is corresponding, i.e. the size of presoma NiFe-LDH reduces, then Ni3The chi of FeN nano particles
It is very little to reduce therewith.
OER overpotentials are lower in table, and activity is higher, and ORR half wave potentials are higher, and activity is higher.As known from Table 3, with cobalt nitrogen
The consumption of the carbon material of codope increases, and the mass fraction of nickel oxide iron nano-particle reduces in the composite for obtaining：
Ni3The mass fraction scope of FeN in 33.3~66.7wt%, the Ni for obtaining3The OER of FeN/Co, N-NCNF composite and
ORR activity is all higher；When mass ratio is higher than 66.7wt%, Ni3The OER activity of FeN/Co, N-NCNF composite is higher, but
It is that ORR activity is extremely low；When mass ratio is less than 33.3wt%, Ni3The ORR activity of FeN/Co, N-NCNF composite is higher, but
It is that OER activity is extremely low.
The present invention passes through it is demonstrated experimentally that Ni3Ni in FeN/Co, N-NCNF composite3The mass fraction of FeN is 50wt%,
And Ni3When FeN particle sizes are 10~20nm, the Ni for finally giving3OER and the ORR activity of FeN/Co, N-NCNF composite
It is optimal.
Therefore Ni is prepared3, it is necessary to consider raw material proportioning, preparation process and work when FeN/Co, N-NCNF composite
Skill parameter is to Ni3The mass fraction of nickel oxide iron nano-particle and nitridation ferronickel nanometer in FeN/Co, N-NCNF composite
The influence of particle size.
Comparative example 3~4
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in the consumption of the nitrogen co-doped carbon material of cobalt be respectively 2mg, 100mg.
Obtain Ni3FeN/Co, N-NCNF composite, size are as shown in table 2.
Embodiment 10~11
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in time of ultrasonic disperse be respectively 45min, 1h.
The result for finally giving is similar to Example 1.
The present invention the experiment proved that the time of ultrasonic disperse it is too short cause dispersion incomplete, but jitter time is small more than half
When, the composite change for finally giving substantially, does not consider time and cost, and present invention selection is using 30min~1h's
The ultrasonic disperse time.
Embodiment 12~13
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in Co in the nitrogen co-doped carbon material of cobalt, the mol ratio of N, C is respectively：0.5：10:90,5:1:90,
The result for finally giving is similar to Example 1.
The present invention the experiment proved that, Co in the nitrogen co-doped carbon material of cobalt, and the mol ratio of N, C is 0.5~5:1~10:90
It is interior, can obtain Ni3FeN/Co, N-NCNF composite, and the change in size of material is little, but 2:5:Under 90 mol ratios,
The Ni for finally giving3The ORR activity highests of FeN/Co, N-NCNF composite.
Comparative example 5
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in the N content of the nitrogen co-doped carbon material of cobalt be 0 because existing without N defects, it is impossible to which NiFe-LDH is born
It is loaded on carbon material, free growth obtains the NiFe-LDH nanometer sheets of 100-200nm, so as to calcine obtain 100-200nm's
Ni3FeN, it is impossible to obtain Ni3FeN/Co, N-NCNF composite.
Comparative example 6
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in the Co contents of the nitrogen co-doped carbon material of cobalt be 0 because Co-N-C is ORR avtive spots, if without Co
In the presence of the ORR activity of carbon material is low, causes the Ni for finally giving3FeN/Co, N-NCNF composite ORR activity are also low.
Embodiment 14~15
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in Ni (NO3)2·6H2O, Fe (NO3)3·9H2The mol ratio difference 1.28 of O and urea：0.42：150、
1.3：0.42：150.
The result for finally giving is similar to Example 1.
Embodiment 16~17
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in Ni (NO3)2·6H2O, Fe (NO3)3·9H2The mol ratio difference 1.25 of O and urea：0.42：140 Hes
1.25：0.42：160,
The result for finally giving is similar to Example 1.
Comparative example 7
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in Ni (NO3)2·6H2O, Fe (NO3)3·9H2The mol ratio of O and urea is 1.28：0：150、0：0.42：
150, obtain Ni (OH)2/ Co, N-CNF composite, Ni is obtained through calcining3N/Co, N-CNF composite, it is impossible to obtain
Ni3FeN/Co, N-NCNF composite.
Comparative example 8
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in Ni (NO3)2·6H2O, Fe (NO3)3·9H2The mol ratio of O and urea is 1.28：0.6：150, obtain
NiFe-LDH (NiFe atomic ratios 2:1) composite, pure Ni cannot be obtained through calcining3, also there is metal simple-substance in FeN.
Comparative example 9
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in Ni (NO3)2·6H2O, Fe (NO3)3·9H2The mol ratio of O and urea is 0：0.42：150, through calcining
Obtain Fe/Co, N-CNF composites, it is impossible to obtain Ni3FeN/Co, N-NCNF composite.
Comparative example 10
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in Ni (NO3)2·6H2O, Fe (NO3)3·9H2The mol ratio of O and urea is 1.25：0.42：0, due to nothing
OH radical ions are present, reactionless generation, it is impossible to generate NiFe-LDH, so as to Ni cannot be obtained3FeN/Co, N-NCNF composite wood
Material.
Comparative example 11
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in Ni (NO3)2·6H2O, Fe (NO3)3·9H2The mol ratio of O and urea is 1.25：0.42：1500, by
It is too strong in solution alkaline, generation Fe (OH)3, and not NiFe-LDH, so as to Ni cannot be obtained3FeN/Co, N-NCNF composite wood
Material.
The present invention the experiment proved that, Ni (NO3)2·6H2O, Fe (NO3)3·9H2The mol ratio of O and urea 1.25~
1.3：0.42：In 150, Ni can be obtained3FeN/Co, N-NCNF composite, and the change in size of material is little, but mix molten
Presoma Ni (NO in liquid3)2·6H2O and Fe (NO3)3·9H2The mol ratio of O is too high or too low, subsequently will be unable to obtain pure
Ni3FeN particles, and Ni (NO in mixed solution3)2·6H2O and urea mol ratio are too high or too low, then cannot NiFe-LDH, Ni
(NO3)2·6H2O and urea mol ratio are slightly higher or slightly lower, then cannot obtain the NiFe-LDH of small size, cannot further obtain small
The Ni of size3FeN particles.
Embodiment 18~19
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in the volume ratio of mixed solution and organic solvent be respectively 2.8：1,3：1.
The result for finally giving is similar to Example 1.
The present invention the experiment proved that the volume ratio of mixed solution and organic solvent is 2.5~3：In 1, can obtain
Ni3FeN/Co, N-NCNF composite, and material change in size less, but mixed solution and organic solvent volume ratio mistake
Greatly, then the carbon material that cobalt cannot be made nitrogen co-doped is dispersed in solution, cause NiFe-LDH cannot completely growth in situ in
The nitrogen co-doped carbon material of cobalt, obtains the free growing NiFe-LDH in part, and fractional load in the nitrogen co-doped carbon material of cobalt
On NiFe-LDH, finally give Ni3FeN and Ni3The mixture of FeN/Co, N-NCNF, not pure Ni3FeN/Co,N-NCNF。
Embodiment 20~21
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in reaction temperature be respectively 95 DEG C, 98 DEG C.
The result for finally giving is similar to Example 1.
Comparative example 12
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in reaction temperature be 200 DEG C, occur side reaction, it is impossible to NiFe-LDH is obtained, so as to cannot obtain
Ni3FeN/Co,N-NCNF。
Comparative example 13
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in reaction temperature be 60 DEG C, reactionless generation, it is impossible to obtain NiFe-LDH, so as to cannot obtain
Ni3FeN/Co,N-NCNF。
The present invention the experiment proved that, prepare NiFe-LDH/Co, reaction temperature during N-CNF in 95~100 DEG C, equal energy
Obtain Ni3FeN/Co, N-NCNF composite, and the change in size of material is little but too high or too low for temperature, finally cannot
Obtain Ni3FeN/Co, N-NCNF composite.
Embodiment 22~23
A kind of carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt, preparation process is with implementation
Example 1, the difference is that only：
Step 1) in drying temperature be respectively 50 DEG C, 55 DEG C.
The result for finally giving is similar to Example 1.
The present invention the experiment proved that prepare NiFe-LDH/Co, drying temperature during N-CNF can be obtained in 50~60 DEG C
To Ni3FeN/Co, N-NCNF composite, and the change in size of material is little, but temperature is too high, it is impossible to obtain Ni3FeN/Co,
N-NCNF composites.
Comparative example 14
Only with Ni3FeN is used as catalyst and cell negative electrode material, and application method is with embodiment 1.
Result shows：There is no the carbon material that cobalt is nitrogen co-doped, independent Ni3FeN only has certain OER activity, ORR activity
Very low, corresponding in battery, charging voltage is low, and discharge voltage is also low, illustrates that the battery storage energy efficiency is high, but cannot be just
Often release energy and use.
Comparative example 15
The only nitrogen co-doped carbon material of cobalt is used as catalyst and cell negative electrode material, and application method is with embodiment 1.
Result shows：The nitrogen co-doped carbon material of pure cobalt, only has certain ORR activity, and OER activity is very low, correspondence
In battery, charging voltage is high, and discharge voltage is also high, illustrates that the battery storage energy efficiency is low, can only be used as disposable electric discharge
Battery is used.
Conclusion：As the nitrogen co-doped carbon material of the cobalt of carrier and being carried on nano silicon nitride ferronickel on carbon material in the present invention
Between cooperate, synergy, not only improve nitridation ferronickel building-up process be easy to reunite, avtive spot cannot be fully sudden and violent
The problem of dew, and influence cobalt nitrogen co-doped carbon material redox reaction activity in itself, therefore answering of finally giving
Condensation material as the catalyst of dioxygen oxidation reduction reaction, and can be applied to the negative pole of zinc-air battery.The present invention is by adjustment
Each technological parameter adjusts the load capacity and particle chi of nano silicon nitride ferronickel in raw material proportioning, implementation steps and preparation process
It is very little, lack the nano silicon nitride ferronickel of carbon carrier or load, the nano silicon nitride ferronickel of load particle size is too high or too low, load
Nano silicon nitride ferronickel it is excessive or very few can all make the material for finally giving have different degrees of decrease in some aspects.The present invention
The carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of cobalt not only shown in OER and ORR reactions
The oxygen catalytic oxidation reduction reaction characteristic of excellent activity, and can be used as efficient zinc-air battery negative material.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all of implementation method cannot be exhaustive here, it is every to belong to this hair
Obvious change that bright technical scheme is extended out changes row still in protection scope of the present invention.
Claims (10)
1. the carrier loaded nano silicon nitride ferronickel composite of the nitrogen co-doped nitrogen carbon material of a kind of cobalt, it is characterised in that described
Composite is with the nitrogen co-doped carbon material of cobalt as carrier；The surface in situ load nickel oxide of the nitrogen co-doped carbon material of the cobalt
Iron nano-particle.
2. the carrier loaded nano silicon nitride ferronickel composite wood of the nitrogen co-doped nitrogen carbon material of a kind of cobalt according to claim 1
Material, it is characterised in that the mass percent of nickel oxide iron nano-particle is 33.3~66.7wt% in the composite；It is described
The size of nickel oxide iron nano-particle is 10~200nm.
3. a kind of carrier loaded nano silicon nitride ferronickel of the nitrogen co-doped nitrogen carbon material of cobalt as described in claim 1,2 is any is answered
The preparation method of condensation material, it is characterised in that comprise the following steps：
1) the nitrogen co-doped carbon material of cobalt is added and contains Ni (NO in after organic solvent for ultrasonic dispersion3)2·6H2O, Fe
(NO3)3·9H2The mixed solution of O and urea, is dried to obtain the nitrogen co-doped carbon material of cobalt and carries after stirring reaction after washing, centrifugation
The nanometer nickel-ferric spinel composite of body load.
2) by step 1) in the material that obtains calcined in ammonia atmosphere after to obtain the nitrogen co-doped nitrogen carbon material of cobalt carrier loaded
Nano silicon nitride ferronickel composite.
4. the carrier loaded nano silicon nitride ferronickel composite wood of the nitrogen co-doped nitrogen carbon material of a kind of cobalt according to claim 3
The preparation method of material, it is characterised in that step 1) described in cobalt nitrogen co-doped carbon material zeolite miaow is protected using silica
The method of azoles ester frame structure material presoma is prepared, the mol ratio of Co, N and C in the nitrogen co-doped carbon material of the cobalt
It is 0.5~5:1~10:90, the organic solvent is dimethyl pyrrolidone, the addition of the nitrogen co-doped carbon material of the cobalt
It is that every milliliter of organic solvent adds the nitrogen co-doped carbon material of the cobalt of 0.625~2.5mg, the time of the ultrasonic disperse is 0.5
~1h.
5. the carrier loaded nano silicon nitride ferronickel composite wood of the nitrogen co-doped nitrogen carbon material of a kind of cobalt according to claim 3
The preparation method of material, it is characterised in that step 1) described in Ni (NO in mixed solution3)2·6H2O、Fe(NO3)3·9H2O and urine
The mol ratio of element is 1.25~1.3：0.42：150, the mixed solution is 2.5~3 with the volume ratio of organic solvent：1.
6. the carrier loaded nano silicon nitride ferronickel composite wood of the nitrogen co-doped nitrogen carbon material of a kind of cobalt according to claim 3
The preparation method of material, it is characterised in that step 1) described in reaction temperature be 95~100 DEG C, the reaction time be 6~8h.
7. the carrier loaded nano silicon nitride ferronickel composite wood of the nitrogen co-doped nitrogen carbon material of a kind of cobalt according to claim 3
The preparation method of material, it is characterised in that step 1) described in wash the solvent for using be second alcohol and water, the drying temperature is 50
~60 DEG C；The drying time is 6~12h.
8. the carrier loaded nano silicon nitride ferronickel composite wood of the nitrogen co-doped nitrogen carbon material of a kind of cobalt according to claim 3
The preparation method of material, it is characterised in that step 3) described in calcining heat be 400~700 DEG C, the calcination time be 1~3h.
9. a kind of carrier loaded nano silicon nitride ferronickel of the nitrogen co-doped nitrogen carbon material of cobalt as described in claim 1,2 is any is answered
Condensation material as the catalyst of electro-catalysis oxygen redox reaction application.
10. a kind of carrier loaded nano silicon nitride ferronickel of the nitrogen co-doped nitrogen carbon material of cobalt as described in claim 1,2 is any
Composite as zinc-air battery negative material application.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107585748A (en) * | 2017-10-11 | 2018-01-16 | 中国科学院理化技术研究所 | A kind of ultra-thin nickel oxide iron composite material of mesoporous silicon oxide protection and its preparation |
| CN107715883A (en) * | 2017-10-26 | 2018-02-23 | 青岛大学 | A kind of Ni3The preparation method of FeN@graphenes/marine alga aeroge elctro-catalyst |
| CN107768645A (en) * | 2017-11-28 | 2018-03-06 | 吉林大学 | A kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material and preparation method thereof |
| CN107824188A (en) * | 2017-10-27 | 2018-03-23 | 广西师范大学 | The preparation method of nickel cobalt layered double hydroxide/graphene elctro-catalyst |
| CN108425131A (en) * | 2018-01-30 | 2018-08-21 | 华东理工大学 | A kind of nickel-molybdenum based alloys being carried on nickel foam and amorphous carbon system and its preparation method and application |
| CN109192996A (en) * | 2018-08-10 | 2019-01-11 | 湘潭大学 | A kind of spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst and its preparation method and application |
| CN109675603A (en) * | 2018-12-28 | 2019-04-26 | 西安交通大学 | A kind of carbon-supported catalysts and its preparation method and application of silica protection |
| CN110459775A (en) * | 2019-08-12 | 2019-11-15 | 苏州大学 | Light inorganic element doping nickel-base material and the preparation method and application thereof |
| CN111041022A (en) * | 2019-11-25 | 2020-04-21 | 浙江大学 | Method for promoting biological methane preparation by using cobalt-nickel zeolite imidazole ester skeleton derived porous carbon |
| CN111151283A (en) * | 2020-01-15 | 2020-05-15 | 中南大学 | Nitrogen-cobalt co-doped porous carbon loaded sulfur-zinc-cobalt catalytic material and preparation method and application thereof |
| CN112206805A (en) * | 2020-10-14 | 2021-01-12 | 扬州大学 | Hollow iron-nickel nitride catalyst, preparation method and all-water electrolysis application thereof |
| CN114164445A (en) * | 2021-12-30 | 2022-03-11 | 青岛科技大学 | V-Ni constructed based on doping and heterojunction strategies3FeN/Ni @ N-GTs full-electrolysis water-electric catalyst |
| CN114672843A (en) * | 2022-03-31 | 2022-06-28 | 山东建筑大学 | Nickel nitride/ruthenium/nitrogen-doped coal activated carbon composite material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140333264A1 (en) * | 2011-02-18 | 2014-11-13 | The Board Of Trustees Of The Leland Stanford Junior University | Battery with hybrid electrocatalysts |
| CN105080550A (en) * | 2015-06-03 | 2015-11-25 | 博天环境集团股份有限公司 | Preparation method for ozonation catalyst for treating coal gasification wastewater |
| CN105514450A (en) * | 2015-12-20 | 2016-04-20 | 青岛科技大学 | Nitrogen-doped graphene-ferronickel hydrotalcite difunctional oxygen catalyst and preparation method and application thereof |
| CN105618060A (en) * | 2015-12-20 | 2016-06-01 | 青岛科技大学 | Bi-functional oxygen catalyst for graphene/nickel iron type hydrotalcite as well as preparation method and application thereof |
-
2017
- 2017-03-22 CN CN201710172269.1A patent/CN106887576B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140333264A1 (en) * | 2011-02-18 | 2014-11-13 | The Board Of Trustees Of The Leland Stanford Junior University | Battery with hybrid electrocatalysts |
| CN105080550A (en) * | 2015-06-03 | 2015-11-25 | 博天环境集团股份有限公司 | Preparation method for ozonation catalyst for treating coal gasification wastewater |
| CN105514450A (en) * | 2015-12-20 | 2016-04-20 | 青岛科技大学 | Nitrogen-doped graphene-ferronickel hydrotalcite difunctional oxygen catalyst and preparation method and application thereof |
| CN105618060A (en) * | 2015-12-20 | 2016-06-01 | 青岛科技大学 | Bi-functional oxygen catalyst for graphene/nickel iron type hydrotalcite as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIA X ,ZHAO Y 等: "Ni3FeN Nanoparticles Derived from Ultrathin NiFe‐Layered Double Hydroxide Nanosheets：An Efficient Overall Water Splitting Electrocatalyst", 《ADVANCED ENERGY MATERIALS》 * |
| LU SHANG，HUIJUN YU等: "Well-Dispersed ZIF-Derived Co,N-Co-doped Carbon Nanoframes through Mesoporous-Silica-Protected Calcination as Efficient Oxygen Reduction Electrocatalysts", 《ADVANCED MATERIALS》 * |
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