CN110504459B - Cobalt sulfide/nitrogen doped mesoporous carbon material and preparation method and application thereof - Google Patents

Cobalt sulfide/nitrogen doped mesoporous carbon material and preparation method and application thereof Download PDF

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CN110504459B
CN110504459B CN201910692171.8A CN201910692171A CN110504459B CN 110504459 B CN110504459 B CN 110504459B CN 201910692171 A CN201910692171 A CN 201910692171A CN 110504459 B CN110504459 B CN 110504459B
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mesoporous carbon
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cobalt
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乔锦丽
刘聪
刘佳闻
王永霞
郭佳宁
王旭
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Donghua University
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Abstract

The invention discloses a preparation method of a cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) with dual-functional activity, which adopts a one-pot method to prepare a mesoporous carbon material with oxygen reduction and oxygen precipitation reactions in one step. Namely, a high polymer containing nitrogen and sulfur elements is used as an organic precursor, ferrous sulfate heptahydrate and cobalt sulfate heptahydrate are used as metal precursors, the organic precursor and the metal precursors are uniformly mixed under the assistance of a solvent, and the nitrogen-doped mesoporous carbon material loaded in situ by CoSx with the size of 2-5nm can be obtained through high-temperature carbonization in an inert atmosphere. Under the blending action of bimetal, the method can effectively inhibit the agglomeration of cobalt on one hand, and synchronously generate nitrogen active sites with efficient catalytic oxygen reduction and cobalt sulfide particles with oxygen evolution activity on a mesoporous carbon substrate on the other hand, and the finally obtained mesoporous carbon material can realize long-time and high-stability charge and discharge circulation when used on a zinc-air battery.

Description

Cobalt sulfide/nitrogen doped mesoporous carbon material and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation and application of a bifunctional catalyst for electrochemical reduction/precipitation of oxygen, and particularly relates to a preparation method and application of a cobalt sulfide/nitrogen-doped mesoporous carbon material.
Background
At present, the contradiction between the gradual exhaustion of energy and the rapid development of human society inevitably leads to the outbreak of various environmental problems, and the development of novel, clean and efficient energy which can meet the requirements of sustainable development is urgent. Among them, electrochemical energy represented by a rechargeable zinc-air battery has attracted much attention because of its advantages such as low cost, environmental friendliness, and high energy density. However, the most important factor hindering the development of zinc air cells is the development and utilization of cathode catalysts (air electrodes) [ j-7134(2016)]. Cathode catalysts such as platinum carbon (Pt/C), ruthenium dioxide (RuO) that have been commercialized to date 2 ) Iridium dioxide (IrO) 2 ) The zinc-air battery belongs to the category of noble metals, and has the problems of low yield, high price and the like, thereby seriously limiting the wide application of the zinc-air battery. Based on this, researchers have attempted to develop low-cost, high-activity and high-stability non-noble metal catalysts to replace the current noble metal catalysts. Various catalysts using transition metals as precursors, such as: transition metal oxides, transition metal sulfides, transition metal nitrides, and the like have attracted attention because of having a bifunctional property of oxygen reduction/oxygen evolution (ORR/OER). Among them, transition metal oxides have been widely studied and some catalysts have exhibited excellent properties. However, these catalysts still have problems such as complicated preparation process, low conductivity, poor stability, etc., so that they must rely on some carbonaceous substrates in preparation applications, including, for example: carbon nanotubes, nanorods, nanowires, graphene, etc. to enhance their current, these limitations make them difficult to put into mass production and utilization [ Carbon,75,5-42 (2014)]. Transition metal sulfides, such as nickel sulfide (NiS), manganese sulfide (MnS), and cobalt sulfide (CoS), etc., are reported to have oxygen evolution/hydrogen evolution (OER/HER) properties compared to transition metal oxides. This shows that the catalyst is expected to have certain potential in rechargeable zinc-air batteries, especially cobalt-based sulfide (CoSx) is considered to have relatively higher oxygen evolution activity because of multiple oxidation states [ J.power sources,390,224-233 (2018)]. In addition, compared with oxides, transition metal sulfides have higher chemical stability and conductivity, but have the problems of complex preparation process, easy agglomeration of metal sulfide particles in the preparation process and the like.
The porous carbon material is widely reported in the preparation of oxygen reduction cathode catalysts, and is a carbonaceous material with high specific surface area, and the huge specific surface area of the porous carbon material can expose a large number of oxygen reduction active sites, so that the reduction utilization of oxygen can be greatly promoted. A large number of literature reports indicate that non-noble metal modified nitrogen-doped porous carbon materials, especially mesoporous materials, have electrocatalytic oxygen reduction performance comparable to commercial platinum-carbon catalysts, but have poor electrocatalytic oxygen evolution capability [ nat. Nanotechnol,10,444-452 (2015) ].
Disclosure of Invention
The invention aims to provide a cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) with bifunctional activity, a preparation method and application thereof, aiming at the defects of the prior art.
In order to achieve the aim, the invention provides a preparation method of a cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC), which is characterized by comprising the following steps of:
step 1: adding the silicon dioxide nano microspheres into HCl solution, stirring the mixture into paste, and placing the paste into an ultrasonic machine for ultrasonic oscillation to obtain uniformly dispersed silicon dioxide template agent;
step 2: adding polyquaternium into HCl solution and stirring uniformly to obtain polyquaternium solution;
and step 3: under the condition of magnetic stirring, feSO 4 ·7H 2 O and/or CoSO 4 ·7H 2 Dissolving O in HCl solution, adding the solution into the polyquaternary ammonium salt solution obtained in the step 2, stirring the solution uniformly, then adding the solution into the silicon dioxide template obtained in the step 1, and stirring the solution uniformly to obtain mixed solution;
and 4, step 4: placing the mixed solution obtained in the step 3 in a forced air drying oven for drying, grinding the dried solid sample into powder, carbonizing at high temperature under the condition of nitrogen, and naturally cooling to room temperature to obtain a black powder sample;
and 5: washing the black powder sample obtained in the step 4 with NaOH solution, washing the sample to be neutral, drying the sample, and then using H 2 SO 4 Acid washing, then washing the sample to neutrality and drying;
step 6: and (3) burning the sample dried in the step (5) at a high temperature under the condition of nitrogen, removing impurities, and naturally cooling to room temperature to obtain the cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC).
Preferably, the mass-to-volume ratio of the silica nanospheres to the HCl solution in step 1 is 0.25-0.5 g/mL.
Preferably, the particle size of the silica nanospheres in step 1 is 100-500 nm.
Preferably, the mass-to-volume ratio of the polyquaternium to the HCl solution in the step 2 is 0.35-0.4 g/mL, and the polyquaternium is polyquaternium 44.
Preferably, the mass ratio of the polyquaternium in the step 2 to the silica nanospheres in the step 1 is 1.125.
Preferably, in the step 3, feSO is used as the catalyst 4 ·7H 2 O and CoSO 4 ·7H 2 When O is added together, feSO 4 ·7H 2 O and CoSO 4 ·7H 2 The mass ratio of O is (2-6) to 1.
Preferably, the FeSO in step 3 4 ·7H 2 The mass-volume ratio of O to HCl solution is 0.15-0.3 g/mL, and CoSO 4 ·7H 2 The mass volume ratio of the O to the HCl solution is 0.05-0.1 g/mL.
Preferably, the concentration of the HCl solution in the steps 1 to 3 is 1mol/L.
Preferably, in the step 4, the drying temperature is 80-100 ℃, the drying time is 24-48 h, and the high-temperature carbonization conditions are as follows: under the condition of nitrogen, the temperature is raised to 800 ℃ at the speed of 20 ℃/min, and the temperature is kept for 1h.
Preferably, the concentration of the NaOH solution in the step 5 is 3-5 mol/L, and the alkaline washing time is 48h, so as to remove the template agent.
Preferably, said step 5 is H 2 SO 4 The concentration of the solution is 0.5-1 mol/L, and the acid washing time is 8h.
Preferably, the high-temperature burning conditions in step 6 are as follows: under the condition of nitrogen, the temperature is raised to 800 ℃ at the speed of 20 ℃/min, and the temperature is kept for 1h.
The invention also provides a cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) prepared by the method.
Preferably, the cobalt sulfide/nitrogen doped mesoporous carbon material is a cobalt-based sulfide in-situ loaded nitrogen doped mesoporous carbon material with the size of 2-5nm, and the cobalt-based sulfide has oxygen evolution/hydrogen evolution catalytic activity.
The invention also provides application of the cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) in preparation of a zinc-air battery cathode catalyst.
The invention provides a brand-new preparation method, namely loading cobalt sulfide nanoparticles on the surface of a mesoporous carbon material to form double active sites to synchronously improve the electrocatalytic oxygen reduction and oxygen evolution capacities of a composite material.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a simple one-pot method to obtain the ORR/OER composite material in one step, thereby avoiding the complex and high-energy consumption process of firstly preparing a metal sulfide material and then loading the metal sulfide material on a carbon substrate by utilizing high temperature and high pressure. By using a high polymer containing nitrogen and sulfur elements as a carbon source, a nitrogen source and a sulfur source, preparing a precursor solution, introducing cobalt salt, carbonizing, preparing a mesoporous carbon material with rich apertures, and growing metal sulfide particles on the surface in situ. The preparation process is clean and environment-friendly, has high repeatability and can be prepared in a large scale.
(2) Aiming at the characteristic that metal sulfide particles are easy to agglomerate, iron salt is added in the process of preparing a precursor solution, and the introduction of the iron salt effectively inhibits the agglomeration of cobalt to form nanometer cobalt sulfide particles with ultra-small particle size (2-5 nm), so that the defects that a catalyst synthesized by single doping of cobalt is easy to agglomerate and has poor performance are avoided.
(3) According to the invention, the iron salt is added in the preparation process of the nitrogen-doped carbon material, so that the carbon precursor is promoted to form more oxygen reduction active sites in the high-temperature carbonization process. Therefore, the prepared cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) has excellent bifunctional characteristics, and shows high stability and cycle performance when applied to a zinc-air battery.
(4) The synthesized cobalt sulfide/nitrogen-doped mesoporous carbon material can realize long-time constant-current discharge when being used for a disposable zinc-air battery, and can continuously discharge for more than 90 hours at a current density of 5 milliamperes; the lithium-ion battery can realize super-long charge-discharge cycle and can still stably run after 1288 charge-discharge cycles (200 hours) are realized.
Drawings
FIG. 1 is a flow chart of the synthesis and preparation of bifunctional CoSx @ NMC.
In FIG. 2, (a) FeSO is used 4 ·7H 2 TEM image of the target product obtained with O as metal precursor (example 2); (b) Using CoSO 4 ·7H 2 TEM image of the target product obtained with O as metal precursor (example 3); (c) Using FeSO 4 ·7H 2 O and CoSO 4 ·7H 2 TEM image of the target product obtained with O as common metal precursor (example 1).
In FIG. 3, (a) FeSO is used 4 ·7H 2 Charge and discharge schematic of O as metal precursor to prepare catalyst (example 2); (b) Using CoSO 4 ·7H 2 Charge and discharge schematic of O as metal precursor to prepare catalyst (example 3); (c) Using FeSO 4 ·7H 2 O and CoSO 4 ·7H 2 Charge and discharge schematic of O as metal precursor to prepare catalyst (example 1).
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
And (3) performance determination: the microscopic morphology of the product of the examples of the present invention was tested by TEM (JEOL JEM-2100F system), SEM (Hitachi S-4800), elemental analysis was determined by XPS (RBDupgrad PHIE5000C ECSA system (Perkinelmer)), half cell performance tests were performed by a three electrode system on Chenghua CHI760D electrochemical workstation, single cell tests were performed on CT2001A blue cell test system.
The manufacturers and specifications of the reagents used in the embodiment of the invention are as follows, ferrous sulfate heptahydrate, cobalt sulfate heptahydrate, hydrochloric acid and sulfuric acid are purchased from Shanghai pharmaceutical group chemical reagent company, polyquaternium-44 is purchased from Sigma-Aldrich company, and nano silicon dioxide (500 nm) is purchased from Hangzhou Wanjing New Material company.
Example 1
The embodiment provides a preparation method of a cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) with bifunctional activity, as shown in FIG. 1, the preparation method specifically comprises the following steps:
step 1: putting 5g of silicon dioxide nano silicon spheres (500 nm) into a 100mL beaker, adding 15mL of HCl solution with the concentration of 1M, stirring into paste, and ultrasonically oscillating to obtain a uniformly dispersed silicon dioxide template agent;
step 2: putting 5.625g of polyquaternium 44 in a 100mL beaker, adding 15mL of 1M HCl, and fully stirring to uniformly disperse the HCl to obtain a polyquaternium 44 solution;
and step 3: under the condition of magnetic stirring, 3.75g of FeSO 4 ·7H 2 O and 1.79g CoSO 4 ·7H 2 Dissolving O in 20mL of 1M HCl, fully dissolving, slowly adding the solution into the polyquaternium 44 solution obtained in the step 2, stirring to uniformly disperse the polyquaternium, adding the obtained mixed solution into the silica template obtained in the step 1, and stirring for 5 hours to fully mix the mixed solution with the template to obtain a final mixed solution;
and 4, step 4: placing the final mixed solution obtained in the step 3 in a forced air drying oven, drying for 48h at 85 ℃, grinding the dried solid sample in an agate mortar for 0.5-2h to obtain powder, heating to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain a black powder sample;
and 5: transferring the black powder sample obtained in the step 4 into 100mL of NaOH solution with the concentration of 4M, alkali washing for 48 hours under magnetic stirring to remove the template agent, washing the sample after the alkali washing to be neutral by using deionized water, drying for 12-24 hours in a forced air drying oven at the temperature of 85 ℃, and then using 50mL of 0.5M H 2 SO 4 Magnetically stirring and pickling for 8h at the temperature of 60 ℃, washing the pickled sample to be neutral by using deionized water, and drying for 12h at the temperature of 85 ℃ in an air-blast drying oven;
and 6: and (3) heating the sample dried in the step (5) to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain the cobalt sulfide/nitrogen-doped mesoporous carbon material (CoSx @ NMC).
Example 2
The embodiment provides a preparation method of a cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) with dual-function activity, as shown in figure 1, the specific preparation steps are as follows:
step 1: adding 5g of silicon dioxide nano silicon spheres (500 nm) into a 100mL beaker, adding 15mL of HCl solution with the concentration of 1M, stirring the mixture into paste by using a glass rod, and then carrying out ultrasonic oscillation to obtain a uniformly dispersed silicon dioxide template agent;
step 2: putting 5.625g of polyquaternium 44 in a 100mL beaker, adding 15mL of 1M HCl, and fully stirring to uniformly disperse the HCl to obtain a polyquaternium 44 solution;
and step 3: under the condition of magnetic stirring, 5.625g of FeSO 4 ·7H 2 Dissolving O in 20mL of 1M HCl, fully dissolving, slowly adding the solution into the polyquaternium 44 solution obtained from the solution in the step 2, stirring to uniformly disperse the polyquaternium 44 solution, then adding the obtained mixed solution into the silicon dioxide template obtained from the step 1, and stirring for 5 hours to fully mix the silicon dioxide template with the silicon dioxide template to obtain a final mixed solution;
and 4, step 4: placing the final mixed solution obtained in the step 3 in a forced air drying oven, drying at 85 ℃ for 48h, grinding the dried solid sample in an agate mortar for 0.5-2h to obtain powder, heating to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain a black powder sample;
and 5: transferring the black powder sample obtained in the step 4 into 100mL of NaOH solution with the concentration of 4M, alkali washing for 48 hours under magnetic stirring to remove the template agent, washing the sample after the alkali washing to be neutral by using deionized water, drying for 12-24 hours in a forced air drying oven at the temperature of 85 ℃, and then using 50mL of 0.5M H 2 SO 4 Pickling for 8h under the condition of 60 ℃ by magnetic stirring. Washing the acid-washed sample with deionized water to neutrality and drying the sample in a forced air drying oven at 85 ℃ for 12 hours;
and 6: and (3) heating the sample dried in the step (5) to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain the cobalt sulfide/nitrogen-doped mesoporous carbon material (CoSx @ NMC).
Example 3
The embodiment provides a preparation method of a cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) with bifunctional activity, as shown in FIG. 1, the preparation method specifically comprises the following steps:
step 1: putting 5g of silicon dioxide nano silicon spheres (500 nm) into a 100mL beaker, adding 15mL of HCl solution with the concentration of 1M, stirring the mixture into paste by using a glass rod, and then carrying out ultrasonic oscillation to obtain a uniformly dispersed silicon dioxide template agent;
and 2, step: putting 5.625g of polyquaternium 44 in a 100mL beaker, adding 15mL of 1M HCl, and fully stirring to uniformly disperse the HCl to obtain a polyquaternium 44 solution;
and step 3: under magnetic stirring, 5.36g CoSO 4 ·7H 2 Dissolving O in 20mL of 1M HCl, fully dissolving, slowly adding the solution into the polyquaternium 44 solution obtained in the step (2), stirring to uniformly disperse the polyquaternium, adding the obtained mixed solution into the silica template obtained in the step (1), and stirring for 5 hours to fully mix the mixed solution with the template to obtain a final mixed solution;
and 4, step 4: placing the final mixed solution obtained in the step 3 in a forced air drying oven, drying at 85 ℃ for 48h, grinding the dried solid sample in an agate mortar for 0.5-2h to obtain powder, heating to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain a black powder sample;
and 5: transferring the black powder sample obtained in the step 4 into 100mL of NaOH solution with the concentration of 4M, alkali washing for 48H under magnetic stirring to remove the template agent, washing the sample after alkali washing to be neutral by using deionized water, drying for 12-24H in a forced air drying oven at the temperature of 85 ℃, and then using 50mL of 0.5M H 2 SO 4 Pickling for 8h under the condition of 60 ℃ by magnetic stirring. Washing the acid-washed sample with deionized water to be neutral and drying the sample in a forced air drying oven at the temperature of 85 ℃ for 12 hours;
step 6: and (3) heating the sample dried in the step (5) to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain the cobalt sulfide/nitrogen-doped mesoporous carbon material (CoSx @ NMC).
Example 4
The embodiment provides a preparation method of a cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) with dual-function activity, as shown in figure 1, the specific preparation steps are as follows:
step 1: putting 5g of silicon dioxide nano silicon spheres (500 nm) into a 100mL beaker, adding 15mL of HCl solution with the concentration of 1M, stirring the mixture into paste by using a glass rod, and then carrying out ultrasonic oscillation to obtain a uniformly dispersed silicon dioxide template agent;
step 2: putting 5.625g of polyquaternium 44 in a 100mL beaker, adding 15mL of 1M HCl, and fully stirring to uniformly disperse the HCl to obtain a polyquaternium 44 solution;
and step 3: under the condition of magnetic stirring, 4.5g of FeSO 4 ·7H 2 O and 1.07g CoSO 4 ·7H 2 Dissolving O in 20mL of 1M HCl, fully dissolving, slowly adding the O into the polyquaternium 44 solution obtained in the step 2, stirring to uniformly disperse the O, then adding the obtained mixed solution into the silicon dioxide template obtained in the step 1, and stirring for 5 hours to fully mix the O with the template to obtain a final mixed solution;
and 4, step 4: placing the final mixed solution obtained in the step 3 in a forced air drying oven, drying for 48h at 85 ℃, grinding the dried solid sample in an agate mortar for 0.5-2h to obtain powder, heating to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain a black powder sample;
and 5: transferring the black powder sample obtained in the step 4 into 100mL of NaOH solution with the concentration of 4M, alkali washing for 48 hours under magnetic stirring to remove the template agent, washing the sample after the alkali washing to be neutral by using deionized water, drying for 12-24 hours in a forced air drying oven at the temperature of 85 ℃, and then using 50mL of 0.5M H 2 SO 4 Pickling for 8h under the condition of 60 ℃ by magnetic stirring. Washing the acid-washed sample with deionized water to be neutral and drying the sample in a forced air drying oven at the temperature of 85 ℃ for 12 hours;
and 6: and (3) heating the sample dried in the step (5) to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain the cobalt sulfide/nitrogen-doped mesoporous carbon material (CoSx @ NMC).
Example 5
The embodiment provides a preparation method of a cobalt sulfide/nitrogen doped mesoporous carbon material (CoSx @ NMC) with bifunctional activity, as shown in FIG. 1, the preparation method specifically comprises the following steps:
step 1: putting 5g of silicon dioxide nano silicon spheres (500 nm) into a 100mL beaker, adding 15mL of HCl solution with the concentration of 1M, stirring the mixture into paste by using a glass rod, and then carrying out ultrasonic oscillation to obtain a uniformly dispersed silicon dioxide template agent;
step 2: putting 5.625g of polyquaternium 44 in a 100mL beaker, adding 15mL of 1M HCl, and fully stirring to uniformly disperse the HCl to obtain a polyquaternium 44 solution;
and step 3: under the condition of magnetic stirring, 5.625g of FeSO 4 ·7H 2 O and 1.07g CoSO 4 ·7H 2 Dissolving O in 20mL of 1M HCl, fully dissolving, slowly adding the solution into the polyquaternium 44 solution obtained in the step 2, stirring to uniformly disperse the polyquaternium, adding the obtained mixed solution into the silica template obtained in the step 1, and stirring for 5 hours to fully mix the mixed solution with the template to obtain a final mixed solution;
and 4, step 4: placing the final mixed solution obtained in the step 3 in a forced air drying oven, drying at 85 ℃ for 48h, grinding the dried solid sample in an agate mortar for 0.5-2h to obtain powder, heating to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain a black powder sample;
and 5: transferring the black powder sample obtained in the step 4 into 100mL of NaOH solution with the concentration of 4M, alkali washing for 48 hours under magnetic stirring to remove the template agent, washing the sample after the alkali washing to be neutral by using deionized water, drying for 12-24 hours in a forced air drying oven at the temperature of 85 ℃, and then using 50mL of 0.5M H 2 SO 4 Pickling for 8h under the condition of 60 ℃ by magnetic stirring. Washing the acid-washed sample with deionized water to neutrality and drying the sample in a forced air drying oven at 85 ℃ for 12 hours;
step 6: and (3) heating the sample dried in the step (5) to 800 ℃ at a heating rate of 20 ℃/min under the condition of nitrogen, maintaining for 1h, and naturally cooling to room temperature to obtain the cobalt sulfide/nitrogen-doped mesoporous carbon material (CoSx @ NMC).
In FIG. 2, (a) 5.625g FeSO are used 4 ·7H 2 TEM image of the target product obtained with O (example 2) as metal precursor (named Fe @ NMC); (b) 5.36g CoSO were used 4 ·7H 2 TEM image of the target product obtained with O (example 3) as metal precursor (named Co @ NMC); (c) 3.75g of FeSO were used 4 ·7H 2 O and 1.79g CoSO 4 ·7H 2 TEM image of the target product obtained with O (example 1) as the common metal precursor (named CoSx @ NMC).
In FIG. 3, (a) 5.625g FeSO are used 4 ·7H 2 Charge and discharge schematic of O (example 2) as metal precursor preparation catalyst (named Fe @ NMC); (b) 5.36g CoSO were used 4 ·7H 2 Charge and discharge schematic of O (example 3) as metal precursor preparation catalyst (named Co @ NMC); (c) 3.75g of FeSO were used 4 ·7H 2 O and 1.79g CoSO 4 ·7H 2 Charge and discharge schematic of O (example 1) as metal precursor preparation catalyst (named cosx @ nmc).
From the TEM image of Fe @ NMC in FIG. 2 (a), a dense and uniform pore structure can be observed, but the presence of metal is hardly seen; the TEM image of co @ nmc in fig. 2 (b) shows that a large amount of bulk cobalt compounds are embedded in the surface of the mesoporous carbon material, and the bulk cobalt compounds block the formed channel structure, so that the channel structure collapses and overlaps, the specific surface area of the mesoporous carbon material is reduced, and the performance of the catalyst is reduced. When iron and cobalt are introduced as a common metal precursor, as shown in TEM of CoSx @ NMC in FIG. 2 (c), the finally formed catalyst product not only has a large specific surface area, but also is embedded with abundant nano cobalt sulfide particles with small particle size on the pore channel. The abundant specific surface area enables a large number of oxygen reduction active sites to be exposed, and the embedded cobalt sulfide nanoparticles can greatly improve the oxygen evolution performance, so that the catalyst synchronously has the double-function characteristics of electrocatalytic oxygen reduction and oxygen evolution.
FIG. 3 is a graph showing the use of Fe @ NMC, co @ NMC and CoSx @ NMC as an avionicThe zinc-air battery made by the electrode has the current density of 1mA cm -2 Charge and discharge curves at time. Compared with catalysts obtained by doping Fe @ NMC and Co @ NMC with single metal, the catalyst CoSx @ NMC obtained by doping with double metals shows the lowest polarization voltage, and the difference between the charging voltage and the discharging voltage is kept at 1.24V (vs. Zn/Zn) after continuously conducting charging and discharging cycles for 200 hours (1288 cycles) + ) On the other hand, it was confirmed to have an ultra-high cycle stability. The excellent difunctional characteristic of CoSx @ NMC is mainly due to the synergistic effect of iron salt and cobalt salt, on one hand, the addition of the iron salt can promote the generation of oxygen reduction active sites (such as pyridine nitrogen, graphite nitrogen and the like), and the cobalt salt is dispersed more uniformly; on the other hand, cobalt sulfide nano-particles with uniform dispersion and smaller particle size are formed in the cobalt salt in the high-temperature process, so that the electrocatalytic oxygen reduction and oxygen evolution performances of the catalyst are synchronously improved.

Claims (7)

1. A preparation method of a cobalt sulfide/nitrogen doped mesoporous carbon material is characterized by comprising the following steps:
step 1: adding the silicon dioxide nano microspheres into HCl solution, stirring the mixture into paste, and placing the paste into an ultrasonic machine for ultrasonic oscillation to obtain uniformly dispersed silicon dioxide template agent;
and 2, step: adding polyquaternium into HCl solution and uniformly stirring to obtain polyquaternium solution, wherein the polyquaternium is polyquaternium 44;
and step 3: under the condition of magnetic stirring, feSO 4 •7H 2 O and CoSO 4 •7H 2 Dissolving O in HCl solution, adding the solution into the polyquaternary ammonium salt solution obtained in the step 2, stirring the solution uniformly, then adding the solution into the silicon dioxide template obtained in the step 1, and stirring the solution uniformly to obtain mixed solution; feSO 4 •7H 2 O and CoSO 4 •7H 2 The mass ratio of O is 2;
and 4, step 4: placing the mixed solution obtained in the step 3 in a forced air drying oven for drying, grinding the dried solid sample into powder, carbonizing at high temperature under the condition of nitrogen, and naturally cooling to room temperature to obtain a black powder sample;
and 5: washing the black powder sample obtained in the step 4 with NaOH solution, washing the sample to be neutral, drying the sample, and then using H 2 SO 4 Acid washing, then washing the sample to neutrality and drying;
step 6: firing the sample dried in the step 5 at a high temperature under the condition of nitrogen, removing impurities, and naturally cooling to room temperature to obtain the cobalt sulfide/nitrogen doped mesoporous carbon material; the high-temperature burning conditions are as follows: under the condition of nitrogen, the temperature is raised to 800 ℃ at the speed of 20 ℃/min, and the temperature is kept for 1h.
2. The method for preparing the cobalt sulfide/nitrogen doped mesoporous carbon material as claimed in claim 1, wherein the mass-to-volume ratio of the silica nanospheres to the HCl solution in the step 1 is 0.25 to 0.5g/mL; the particle size of the silicon dioxide nano-microspheres is 100-500nm.
3. The method for preparing the cobalt sulfide/nitrogen-doped mesoporous carbon material according to claim 1, wherein the mass-to-volume ratio of the polyquaternium to the HCl solution in the step 2 is 0.35 to 0.4g/mL.
4. The method for preparing the cobalt sulfide/nitrogen doped mesoporous carbon material according to claim 1, wherein the mass ratio of the polyquaternium in the step 2 to the silica nanospheres in the step 1 is 1.125.
5. A cobalt sulfide/nitrogen doped mesoporous carbon material prepared by the method of any one of claims 1 to 4.
6. The cobalt sulfide/nitrogen-doped mesoporous carbon material according to claim 5, wherein the material is a 2 to 5 nm-sized cobalt-based sulfide in-situ supported nitrogen-doped mesoporous carbon material, and the cobalt-based sulfide has oxygen evolution/hydrogen evolution catalytic activity.
7. The use of the cobalt sulfide/nitrogen doped mesoporous carbon material of claim 5 in the preparation of a zinc air cell cathode catalyst.
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