CN110504459A - A kind of cobalt sulfide/N doping meso-porous carbon material and the preparation method and application thereof - Google Patents
A kind of cobalt sulfide/N doping meso-porous carbon material and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods with difunctional active cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC), have the meso-porous carbon material of hydrogen reduction and oxygen evolution reaction using the preparation of one step of one kettle way.Use nitrogenous, element sulphur high polymer as organic precursor, green vitriol and Cobalt monosulfate heptahydrate are as metal precursor, organic precursor and metal precursor are uniformly mixed under solvent auxiliary, by high temperature cabonization under an inert atmosphere, the N doping meso-porous carbon material that the CoSx of 2-5nm size is loaded in situ can be obtained.This method is under bimetallic reconciliation effect, on the one hand the reunion of cobalt can effectively be inhibited, on the other hand it is synchronized on mesoporous carbon base body and generates the active sites of the nitrogen with efficient catalytic oxidation-reduction and the cobalt sulfide particle with oxygen evolution activity, finally obtained meso-porous carbon material long-time achievable on zinc and air cell, the charge and discharge cycles of high stability.
Description
Technical field
The invention belongs to oxygen electrochemical reduction/precipitation bifunctional catalyst preparation and application field, in particular to one
Kind cobalt sulfide/N doping meso-porous carbon material preparation method and application.
Background technique
Currently, the contradiction between the increasingly exhausted and human society fast development of the energy has inevitably led to various rings
The outburst of border problem, develop it is novel, cleaning, efficiently and be able to satisfy sustainable development requirement the energy it is extremely urgent.Wherein with can
The electrochemical energy that formula zinc-air battery is representative is filled to cause because having many advantages, such as that at low cost, environmental-friendly, energy density is high
The extensive concern of people.However, hindering zinc and air cell to develop most important factor is then opening for cathod catalyst (air electrode)
Hair utilizes [J.Mater.Chem.A, 4,7107-7134 (2016)].Commercialized cathod catalyst such as platinum carbon is had been carried out at present
(Pt/C), ruthenic oxide (RuO2), iridium dioxide (IrO2) because belonging to noble metal scope, there are low outputs, expensive etc. to ask
Topic, seriously limits the extensive use of zinc and air cell.Based on this, researchers try hard to develop low cost, high activity high stable
The non-precious metal catalyst of property substitutes current noble metal catalyst.Using transition metal as all kinds of catalyst of presoma, such as:
Transition metal oxide, transient metal sulfide, transition metal nitride etc. are double because having hydrogen reduction/oxygen that (ORR/OER) is precipitated
Functional characteristic attracts extensive attention.Wherein, transition metal oxide be widely studied and partial catalyst shown it is excellent
Performance.But this kind of catalyst still suffers from some problems, such as the problems such as preparation process is cumbersome, and conductivity is low, stability is poor,
Therefore it must rely on some carbon paper substrates in application and preparation, including such as: carbon nanotube, carbon nano rod, carbon nanocoils, graphene
Etc. enhancing its electric current, these restrictive conditions make its be difficult to put into large-scale production utilize in [Carbon, 75,5-42
(2014)].Compared to transition metal oxide, transient metal sulfide, such as nickel sulfide (NiS), manganese sulfide (MnS) and cobalt sulfide
(CoS) etc. being reported has analysis oxygen/liberation of hydrogen (OER/HER) performance.This shows that such catalyst is expected in rechargeable type zinc and air cell
It is upper that there are certain potentiality to be considered to have relatively more especially with regard to cobalt-based sulfide (CoSx) because it is with a variety of oxidation state
Active [J.power sources, 390,224-233 (2018)] is precipitated in high oxygen.In addition, transient metal sulfide is compared to oxidation
There is higher chemical stability and conductivity for object, but there are preparation process is cumbersome and preparation process in metal sulfide
The problems such as particle is easy to reunite.
Porous carbon materials, by wide coverage, are a kind of carbon with high-specific surface area on preparing oxygen reduction cathode catalyst
Material, huge specific surface area can expose a large amount of oxygen reduction activity site, thus can greatly facilitate oxygen
Reduction utilizes.Lot of documents report shows that the nitrogen-doped porous carbon material of base metal modification, especially mesoporous material have and be equal to
The electrocatalytic oxidation reducing property of US business's industry platinum carbon catalyst, however its electro-catalysis analysis oxygen ability is very poor
[Nat.nanotechnol,10,444-452(2015)]。
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide one kind, and there is difunctional active cobalt sulfide/nitrogen to mix
Miscellaneous meso-porous carbon material (CoSx@NMC) and the preparation method and application thereof.
In order to achieve the above object, the present invention provides a kind of cobalt sulfide/N doping meso-porous carbon materials (CoSx@NMC)
Preparation method, which comprises the following steps:
Step 1: silicon dioxide nanosphere being added in HCl solution, paste is stirred into and is placed on the shake of ultrasonic machine ultrasound
It swings, obtains finely dispersed silica template agent；
Step 2: polyquaternium being added to HCl solution and is stirred evenly, polyquaternium solution is obtained；
Step 3: under the conditions of magnetic agitation, by FeSO4·7H2O and/or CoSO4·7H2O is dissolved in HCl solution, is added
It in the polyquaternium solution obtained to step 2, is stirred until homogeneous, is then added in the silica template agent that step 1 obtains,
It is stirred until homogeneous, obtains mixed solution；
Step 4: the mixed solution that step 3 is obtained is placed in air dry oven drying, and the solid sample after drying is ground
At powder, high temperature cabonization under a nitrogen atmosphere, then cooled to room temperature, obtains black powder sample；
Step 5: the black powder sample that step 4 obtains first being used into NaOH solution alkali cleaning, then washs sample to neutrality
And it dries, then use H2SO4Then pickling washs sample to neutral and dry；
Step 6: by sample of the step 5 after dry high temperature sintering under a nitrogen atmosphere, removing impurity, cooled to room temperature
Obtain cobalt sulfide/N doping meso-porous carbon material (CoSx NMC) afterwards.
Preferably, the mass volume ratio of silicon dioxide nanosphere and HCl solution is 0.25~0.5g/ in the step 1
mL。
Preferably, the partial size of silicon dioxide nanosphere is 100~500nm in the step 1.
Preferably, in the step 2 polyquaternium and HCl solution 0.35~0.4g/mL of mass volume ratio, the poly- season
Ammonium salt is polyquaternium 44.
Preferably, the mass ratio of polyquaternium and silicon dioxide nanosphere in step 1 is 1.125:1 in the step 2.
Preferably, in the step 3, work as FeSO4·7H2O and CoSO4·7H2When O is added together, FeSO4·7H2O with
CoSO4·7H2The mass ratio of O is (2~6): 1.
Preferably, FeSO in the step 34·7H2The mass volume ratio of O and HCl solution is 0.15~0.3g/mL,
CoSO4·7H2The mass volume ratio of O and HCl solution is 0.05~0.1g/mL.
Preferably, the concentration of HCl solution is 1mol/L in step 1~3.
Preferably, drying temperature is 80~100 DEG C in the step 4, and drying time is 24~48h, high temperature cabonization condition
Are as follows: under a nitrogen atmosphere, 800 DEG C are warming up to 20 DEG C/min rate, keeps the temperature 1h.
Preferably, NaOH solution concentration is 3~5mol/L in the step 5, and the alkali cleaning time is 48h, to remove template agent removing.
Preferably, H in the step 52SO4Solution concentration is 0.5~1mol/L, pickling time 8h.
Preferably, the step 6 high temperature calcination condition are as follows: under a nitrogen atmosphere, be warming up to 800 with 20 DEG C/min rate
DEG C, keep the temperature 1h.
The present invention also provides cobalt sulfide/N doping meso-porous carbon materials (CoSx@NMC) of above method preparation.
Preferably, the cobalt sulfide/N doping meso-porous carbon material is that the cobalt-based sulfide of 2~5nm size loads in situ
N doping meso-porous carbon material, the cobalt-based sulfide have analysis oxygen/catalytic activity for hydrogen evolution.
The present invention also provides above-mentioned cobalt sulfide/N doping meso-porous carbon materials (CoSx@NMC) to prepare zinc and air cell cathode
Application in catalyst.
The invention proposes a kind of completely new preparation methods --- in meso-porous carbon material area load cobalt sulfide nanometer
Grain --- to form the electrocatalytic oxidation reduction and analysis oxygen ability that Synchronous lifting composite material is carried out in double activated position.
The present invention compared with prior art, has the beneficial effect that
(1) present invention obtains ORR/OER composite material using simple " one kettle way " step, and metal will first be prepared by eliminating
Then sulfide material recycles high temperature and pressure to load to the cumbersome and high energy consumption process of carbon base body.By using nitrogenous and sulphur
The high polymer of element introduces cobalt salt after being made into precursor solution as carbon source, nitrogen source and sulphur source, can be made after being carbonized with rich
The meso-porous carbon material in rich aperture, while metal sulfide particle is grown in its surface in situ.Preparation process clean and environmental protection repeats
Property it is high, and being capable of prepare with scale.
(2) feature easy to reunite for metal sulfide grain, the present invention pass through during prepared by precursor solution
Molysite is added, the introducing of molysite effectively inhibits the reunion of cobalt, forms the nanometer cobalt sulfide particle of ultra-small grain size (2-5nm), keeps away
The catalyst for having exempted from the doping synthesis of cobalt list is easy to reunite, performance difference defect.
(3) molysite is added in the present invention in the preparation process of nitrogen-doped carbon material, promotes carbon matrix precursor in high temperature cabonization
More oxygen reduction activity positions are formed in the process.Cobalt sulfide/N doping meso-porous carbon material (the CoSx@NMC) tool thus prepared
There is excellent double function characteristic, and is applied to zinc and air cell and shows very high stability and cycle performance.
(4) cobalt sulfide/N doping meso-porous carbon material that the present invention synthesizes can be realized for a long time for disposable zinc and air cell
Constant-current discharge, can be continuous discharge 90 more than hour under 5 milliamperes of current density；It can be realized for Chargeable zinc-air cell super
Prolonged charge and discharge cycles remain to stable operation after realizing 1288 charge and discharge cycles (200 hours).
Detailed description of the invention
Fig. 1 is synthesis and preparation flow figure with difunctional CoSx@NMC.
In Fig. 2, (a) uses FeSO4·7H2The TEM for the target product (embodiment 2) that O is obtained as metal precursor schemes；
(b) CoSO is used4·7H2The TEM for the target product (embodiment 3) that O is obtained as metal precursor schemes；(c) FeSO is used4·
7H2O and CoSO4·7H2The TEM for the target product (embodiment 1) that O is obtained as common metal presoma schemes.
In Fig. 3, (a) uses FeSO4·7H2O prepares the charge and discharge electrical schematic of catalyst (embodiment 2) as metal precursor
Figure；(b) CoSO is used4·7H2O prepares the charge and discharge electrical schematic of catalyst (embodiment 3) as metal precursor；(c) it uses
FeSO4·7H2O and CoSO4·7H2O prepares the charge and discharge electrical schematic of catalyst (embodiment 1) as metal precursor.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Performance measurement: the microscopic appearance of product of the embodiment of the present invention passes through TEM (JEOL JEM-2100F system), SEM
(Hitachi S-4800) is tested, and elemental analysis utilizes XPS ((RBDupgraded PHIe5000C ECSA system
(PerkinElmer)) it is measured.Half-cell performance test is using three-electrode system in occasion China CHI760D electrochemical operation
It is tested on standing.Monocell test carries out on the blue electric battery test system of CT2001A.
In the embodiment of the present invention using reagent producer and specification it is as follows: green vitriol, Cobalt monosulfate heptahydrate purchase,
Hydrochloric acid and sulfuric acid purchase Shanghai Sinopharm Chemical Reagent Co., Ltd., and polyquaternium -44 purchases U.S. Sigma-Aldrich public affairs
Department, nano silica (500nm) purchase Hangzhou Wanjing New Material Co., Ltd..
Embodiment 1
One kind is present embodiments provided with difunctional active cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC)
Preparation method, as shown in Figure 1, specific preparation process is as follows:
Step 1: by 5g silica nanometer silicon ball (500nm) in 100mL beaker, the HCl that 15mL concentration is 1M is added
Solution stirs into paste and ultrasonic vibration, to obtain finely dispersed silica template agent；
Step 2: by 5.625g polyquaternium 44 in 100mL beaker, the HCl that 15mL concentration is 1M is added and is sufficiently stirred
Keep its evenly dispersed, obtains 44 solution of polyquaternium；
Step 3: under the conditions of magnetic agitation, by 3.75g FeSO4·7H2O and 1.79g CoSO4·7H2O is dissolved in 20mL
Concentration is sufficiently to dissolve in the HCl of 1M, and being slowly added to stirring in 44 solution of polyquaternium obtained to step 2 keeps its dispersion equal
It is even, then obtained mixed solution is added in the silica template agent obtained to step 1 and stirring 5h fills it with template
Divide mixing, obtains final mixed solution；
Step 4: the final mixed solution that step 3 is obtained is placed in air dry oven, and 85 DEG C of dry 48h are complete by drying
Solid sample grinds 0.5-2h in the agate mortar rises to it with the heating rate of 20 DEG C/min under condition of nitrogen gas at powdered
800 DEG C and 1h is maintained, then cooled to room temperature, obtains black powder sample；
Step 5: the black powder sample that step 4 obtains being transferred in the NaOH solution that 100mL concentration is 4M, magnetic force stirs
Lower alkali cleaning 48h is mixed to remove template agent removing, sample being washed with deionized to neutrality and 85 in air dry oven after alkali cleaning
Dry 12-24h, then uses the H of 50mL 0.5M under the conditions of DEG C2SO4Magnetic agitation pickling 8h, sample after pickling under the conditions of 60 DEG C
It is washed with deionized to neutrality and dries 12h under the conditions of 85 DEG C in air dry oven；
Step 6: sample of the step 5 after dry is risen to 800 DEG C simultaneously with the heating rate of 20 DEG C/min under a nitrogen atmosphere
Maintain 1h, after cooled to room temperature, obtain cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC).
Embodiment 2
One kind is present embodiments provided with difunctional active cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC)
Preparation method, as shown in Figure 1, specific preparation process is as follows:
Step 1: by 5g silica nanometer silicon ball (500nm) in 100mL beaker, the HCl that 15mL concentration is 1M is added
Solution, ultrasonic vibration after stirring into paste with glass bar, to obtain finely dispersed silica template agent；
Step 2: by 5.625g polyquaternium 44 in 100mL beaker, the HCl that 15mL concentration is 1M is added and is sufficiently stirred
Keep its evenly dispersed, obtains 44 solution of polyquaternium；
Step 3: under the conditions of magnetic agitation, by 5.625g FeSO4·7H2O is dissolved in the HCl that 20mL concentration is 1M, is filled
Point dissolution, being slowly added in 44 solution of polyquaternium obtained to step 2 solution stirring makes it be uniformly dispersed, and then will obtain
Mixed solution is added in the silica template agent obtained to step 1 and stirring 5h is sufficiently mixed it with template, obtains final
Mixed solution；
Step 4: the final mixed solution that step 3 is obtained is placed in air dry oven, and 85 DEG C of dry 48h are complete by drying
Solid sample grinds 0.5-2h in the agate mortar rises to it with the heating rate of 20 DEG C/min under condition of nitrogen gas at powdered
800 DEG C and 1h is maintained, then cooled to room temperature, obtains black powder sample；
Step 5: the black powder sample that step 4 obtains being transferred in the NaOH solution that 100mL concentration is 4M, magnetic force stirs
Lower alkali cleaning 48h is mixed to remove template agent removing, sample being washed with deionized to neutrality and 85 in air dry oven after alkali cleaning
Dry 12-24h, then uses the H of 50mL 0.5M under the conditions of DEG C2SO4Magnetic agitation pickling 8h under the conditions of 60 DEG C.Sample after pickling
It is washed with deionized to neutrality and dries 12h under the conditions of 85 DEG C in air dry oven；
Step 6: sample of the step 5 after dry is risen to 800 DEG C simultaneously with the heating rate of 20 DEG C/min under a nitrogen atmosphere
Maintain 1h, after cooled to room temperature, obtain cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC).
Embodiment 3
One kind is present embodiments provided with difunctional active cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC)
Preparation method, as shown in Figure 1, specific preparation process is as follows:
Step 1: by 5g silica nanometer silicon ball (500nm) in 100mL beaker, the HCl that 15mL concentration is 1M is added
Solution, ultrasonic vibration after stirring into paste with glass bar, to obtain finely dispersed silica template agent；
Step 2: by 5.625g polyquaternium 44 in 100mL beaker, the HCl that 15mL concentration is 1M is added and is sufficiently stirred
Keep its evenly dispersed, obtains 44 solution of polyquaternium；
Step 3: under the conditions of magnetic agitation, by 5.36g CoSO4·7H2O is dissolved in the HCl that 20mL concentration is 1M, sufficiently
Dissolution, being slowly added into 44 solution of polyquaternium of step 2 stirring makes it be uniformly dispersed, and then adds obtained mixed solution
Enter in the silica template agent obtained to step 1 and stirring 5h is sufficiently mixed it with template, obtains final mixed solution；
Step 4: the final mixed solution that step 3 is obtained is placed in air dry oven, and 85 DEG C of dry 48h are complete by drying
Solid sample grinds 0.5-2h in the agate mortar rises to it with the heating rate of 20 DEG C/min under condition of nitrogen gas at powdered
800 DEG C and 1h is maintained, then cooled to room temperature, obtains black powder sample；
Step 5: the black powder sample that step 4 obtains being transferred in the NaOH solution that 100mL concentration is 4M, magnetic force stirs
Lower alkali cleaning 48h is mixed to remove template agent removing, sample being washed with deionized to neutrality and 85 in air dry oven after alkali cleaning
Dry 12-24h, then uses the H of 50mL 0.5M under the conditions of DEG C2SO4Magnetic agitation pickling 8h under the conditions of 60 DEG C.Sample after pickling
It is washed with deionized to neutrality and dries 12h under the conditions of 85 DEG C in air dry oven；
Step 6: sample of the step 5 after dry is risen to 800 DEG C simultaneously with the heating rate of 20 DEG C/min under a nitrogen atmosphere
Maintain 1h, after cooled to room temperature, obtain cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC).
Embodiment 4
One kind is present embodiments provided with difunctional active cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC)
Preparation method, as shown in Figure 1, specific preparation process is as follows:
Step 1: by 5g silica nanometer silicon ball (500nm) in 100mL beaker, the HCl that 15mL concentration is 1M is added
Solution, ultrasonic vibration after stirring into paste with glass bar, to obtain finely dispersed silica template agent；
Step 2: by 5.625g polyquaternium 44 in 100mL beaker, the HCl that 15mL concentration is 1M is added and is sufficiently stirred
Keep its evenly dispersed, obtains 44 solution of polyquaternium；
Step 3: under the conditions of magnetic agitation, by 4.5g FeSO4·7H2O and 1.07g CoSO4·7H2It is dense that O is dissolved in 20mL
Degree is sufficiently to dissolve in the HCl of 1M, being slowly added to stirring in 44 solution of polyquaternium obtained to step 2 keeps its dispersion equal
It is even, then obtained mixed solution is added in the silica template agent obtained to step 1 and stirring 5h fills it with template
Divide mixing, obtains final mixed solution；
Step 4: the final mixed solution that step 3 is obtained is placed in air dry oven, and 85 DEG C of dry 48h are complete by drying
Solid sample grinds 0.5-2h in the agate mortar rises to it with the heating rate of 20 DEG C/min under condition of nitrogen gas at powdered
800 DEG C and 1h is maintained, then cooled to room temperature, obtains black powder sample；
Step 5: the black powder sample that step 4 obtains is transferred in the NaOH solution that 100mL concentration is 4M, magnetic force
Alkali cleaning 48h is under stirring to remove template agent removing, sample being washed with deionized to neutrality and in air dry oven after alkali cleaning
Dry 12-24h, then uses the H of 50mL 0.5M under the conditions of 85 DEG C2SO4Magnetic agitation pickling 8h under the conditions of 60 DEG C.Sample after pickling
Product are washed with deionized to neutrality and dry 12h under the conditions of 85 DEG C in air dry oven；
Step 6: sample of the step 5 after dry is risen to 800 DEG C simultaneously with the heating rate of 20 DEG C/min under a nitrogen atmosphere
Maintain 1h, after cooled to room temperature, obtain cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC).
Embodiment 5
One kind is present embodiments provided with difunctional active cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC)
Preparation method, as shown in Figure 1, specific preparation process is as follows:
Step 1: by 5g silica nanometer silicon ball (500nm) in 100mL beaker, the HCl that 15mL concentration is 1M is added
Solution, ultrasonic vibration after stirring into paste with glass bar, to obtain finely dispersed silica template agent；
Step 2: by 5.625g polyquaternium 44 in 100mL beaker, the HCl that 15mL concentration is 1M is added and is sufficiently stirred
Keep its evenly dispersed, obtains 44 solution of polyquaternium；
Step 3: under the conditions of magnetic agitation, by 5.625g FeSO4·7H2O and 1.07g CoSO4·7H2O is dissolved in 20mL
Concentration is sufficiently to dissolve in the HCl of 1M, and being slowly added to stirring in 44 solution of polyquaternium obtained to step 2 keeps its dispersion equal
It is even, then obtained mixed solution is added in the silica template agent obtained to step 1 and stirring 5h fills it with template
Divide mixing, obtains final mixed solution；
Step 4: the final mixed solution that step 3 is obtained is placed in air dry oven, and 85 DEG C of dry 48h are complete by drying
Solid sample grinds 0.5-2h in the agate mortar rises to it with the heating rate of 20 DEG C/min under condition of nitrogen gas at powdered
800 DEG C and 1h is maintained, then cooled to room temperature, obtains black powder sample；
Step 5: the black powder sample that step 4 obtains being transferred in the NaOH solution that 100mL concentration is 4M, magnetic force stirs
Lower alkali cleaning 48h is mixed to remove template agent removing, sample being washed with deionized to neutrality and 85 in air dry oven after alkali cleaning
Dry 12-24h, then uses the H of 50mL 0.5M under the conditions of DEG C2SO4Magnetic agitation pickling 8h under the conditions of 60 DEG C.Sample after pickling
It is washed with deionized to neutrality and dries 12h under the conditions of 85 DEG C in air dry oven；
Step 6: sample of the step 5 after dry is risen to 800 DEG C simultaneously with the heating rate of 20 DEG C/min under a nitrogen atmosphere
Maintain 1h, after cooled to room temperature, obtain cobalt sulfide/N doping meso-porous carbon material (CoSx@NMC).
In Fig. 2, (a) uses 5.625g FeSO4·7H2The target product that O (embodiment 2) is obtained as metal precursor
The TEM of (being named as Fe@NMC) schemes；(b) 5.36g CoSO is used4·7H2The mesh that O (embodiment 3) is obtained as metal precursor
Mark the TEM figure of product (being named as Co@NMC)；(c) 3.75g FeSO is used4·7H2O and 1.79g CoSO4·7H2O (embodiment
1) the TEM figure of the target product (being named as CoSx@NMC) obtained as common metal presoma.
In Fig. 3, (a) uses 5.625g FeSO4·7H2O (embodiment 2) prepares catalyst (name as metal precursor
For the charge and discharge electrical schematic of Fe NMC)；(b) 5.36g CoSO is used4·7H2O (embodiment 3) is urged as metal precursor preparation
The charge and discharge electrical schematic of agent (being named as Co NMC)；(c) 3.75g FeSO is used4·7H2O and 1.79g CoSO4·7H2O
(embodiment 1) prepares the charge and discharge electrical schematic of catalyst (being named as CoSx NMC) as metal precursor.
From in Fig. 2 (a) in the TEM figure of Fe@NMC it can be observed that intensive and uniform pore structure, but be hardly visible
The presence of metal；And the TEM chart of Fig. 2 (b) Co@NMC is bright, has a large amount of blocky cobalt compound to be embedded in the table of meso-porous carbon material
Face, these block-like cobalt compounds, which can block, is formed by cellular structure, causes collapsing, the overlapping of cellular structure, reduces Jie
The specific surface area of hole carbon material, so that the reduced performance of catalyst.When introducing iron cobalt as common metal presoma, such as Fig. 2
(c) in shown in the TEM of CoSx@NMC, the catalyst product eventually formed not only possesses biggish specific surface area, but also its duct
On nanometer also embedded with abundant compared with small particle vulcanize cobalt granule.Specific surface area abundant makes a large amount of oxygen reduction activity site
The vulcanization cobalt nano-particle for being exposed, and being embedded with then can significantly promote analysis oxygen performance, this synchronizes catalyst to be provided with
The double function characteristic of electrocatalytic oxidation reduction and analysis oxygen.
Fig. 3 is to use Fe@NMC, Co@NMC and CoSx@NMC as zinc-air battery made of air electrode in electricity respectively
Current density is 1mA cm-2When charging and discharging curve.Using monometallic adulterate obtained catalyst compared to Fe@NMC, Co@NMC and
Speech, the obtained catalyst CoSx@NMC of bimetal-doped show minimum polarizing voltage, are being carried out continuously 200 hours
After the charge and discharge cycles of (1288 circulations), the difference of charging voltage and discharge voltage remains at 1.24V (vs.Zn/Zn+) left and right, it was demonstrated that its cyclical stability with superelevation.CoSx@NMC excellent double function characteristic is primarily due to molysite and cobalt
The collaboration reconciliation of salt acts on, on the one hand, the addition of molysite can promote generation (such as pyridine nitrogen, graphite nitrogen of oxygen reduction activity position
Deng), and it is more uniform that cobalt salt is dispersed；On the other hand, cobalt salt forms be uniformly dispersed in the high temperature process, partial size compared with
Small vulcanization cobalt nano-particle, therefore, electrocatalytic oxidation reduction and the analysis oxygen performance of Synchronous lifting catalyst.
Claims (10)
1. a kind of cobalt sulfide/N doping meso-porous carbon material preparation method, which is characterized in that specifically includes the following steps:
Step 1: silicon dioxide nanosphere being added in HCl solution, paste is stirred into and is placed on ultrasonic machine ultrasonic vibration, obtain
To finely dispersed silica template agent；
Step 2: polyquaternium being added to HCl solution and is stirred evenly, polyquaternium solution is obtained；
Step 3: under the conditions of magnetic agitation, by FeSO4·7H2O and/or CoSO4·7H2O is dissolved in HCl solution, and step is added
It in the polyquaternium solution obtained to 2, is stirred until homogeneous, is then added in the silica template agent that step 1 obtains, stir
To uniform, mixed solution is obtained；
Step 4: the mixed solution that step 3 is obtained is placed in air dry oven drying, and the solid sample after drying is pulverized
End, high temperature cabonization under a nitrogen atmosphere, then cooled to room temperature, obtains black powder sample；
Step 5: the black powder sample that step 4 obtains first being used into NaOH solution alkali cleaning, then sample is washed to neutrality and dried
It is dry, then use H2SO4Then pickling washs sample to neutral and dry；
Step 6: by sample of the step 5 after dry high temperature sintering under a nitrogen atmosphere, removing impurity, after cooled to room temperature i.e.
Obtain cobalt sulfide/N doping meso-porous carbon material.
2. cobalt sulfide as described in claim 1/N doping meso-porous carbon material preparation method, which is characterized in that the step 1
The mass volume ratio of middle silicon dioxide nanosphere and HCl solution is 0.25~0.5g/mL；The partial size of silicon dioxide nanosphere
For 100~500nm.
3. cobalt sulfide as described in claim 1/N doping meso-porous carbon material preparation method, which is characterized in that the step 2
0.35~0.4g/mL of mass volume ratio of middle polyquaternium and HCl solution, the polyquaternium are polyquaternium 44.
4. cobalt sulfide as described in claim 1/N doping meso-porous carbon material preparation method, which is characterized in that the step 2
The mass ratio of silicon dioxide nanosphere is 1.125:1 in middle polyquaternium and step 1.
5. cobalt sulfide as described in claim 1/N doping meso-porous carbon material preparation method, which is characterized in that the step 3
In, work as FeSO4·7H2O and CoSO4·7H2When O is added together, FeSO4·7H2O and CoSO4·7H2The mass ratio of O be (2~
6):1。
6. cobalt sulfide as claimed in claim 5/N doping meso-porous carbon material preparation method, which is characterized in that the step 3
Middle FeSO4·7H2The mass volume ratio of O and HCl solution is 0.15~0.3g/mL, CoSO4·7H2The mass body of O and HCl solution
Product is than being 0.05~0.1g/mL.
7. cobalt sulfide as described in claim 1/N doping meso-porous carbon material preparation method, which is characterized in that the step 6
High temperature calcination condition are as follows: under a nitrogen atmosphere, be warming up to 800 DEG C with 20 DEG C/min rate, keep the temperature 1h.
8. cobalt sulfide/N doping meso-porous carbon material of any one of claim 1~7 the method preparation.
9. cobalt sulfide as claimed in claim 8/N doping meso-porous carbon material, which is characterized in that the material is 2~5nm ruler
The N doping meso-porous carbon material that very little cobalt-based sulfide loads in situ, the cobalt-based sulfide have analysis oxygen/catalytic activity for hydrogen evolution.
10. cobalt sulfide described in claim 8/N doping meso-porous carbon material (CoSx@NMC) is preparing zinc and air cell cathod catalyst
In application.
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