CN114751395B - Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery - Google Patents
Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery Download PDFInfo
- Publication number
- CN114751395B CN114751395B CN202210567983.1A CN202210567983A CN114751395B CN 114751395 B CN114751395 B CN 114751395B CN 202210567983 A CN202210567983 A CN 202210567983A CN 114751395 B CN114751395 B CN 114751395B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- porous carbon
- doped porous
- composite material
- carbon sphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a nitrogen-doped porous carbon sphere/S composite material, a preparation method thereof and application thereof in a lithium-sulfur battery, wherein the preparation of the nitrogen-doped porous carbon sphere/S composite material comprises the following steps: mixing the solution A and the solution B, and reacting in a specific temperature range; separating a solid phase product, washing the solid phase product with deionized water, and drying to obtain white powder; the solution A comprises zinc salt and deionized water; the solution B comprises 2-methylimidazole and deionized water; carbonizing the dried sample to obtain a nitrogen-doped porous carbon sphere material; and uniformly mixing the nitrogen-doped porous carbon spheres with sublimed sulfur, and performing heat treatment to obtain the nitrogen-doped porous carbon sphere/S composite material. According to the invention, through low-temperature regulation and control of water system ZIF coordination behaviors, the nitrogen-doped porous carbon sphere material obtained through heat treatment has good physical and chemical adsorption effects on polysulfide and large specific surface area, can effectively inhibit polysulfide shuttle effect, reduce positive electrode electron transmission resistance, relieve volume change of charge and discharge products, improve sulfur utilization rate, and finally obtain the lithium-sulfur battery with long-cycle stability.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a nitrogen-doped porous carbon sphere/S composite material, a preparation method thereof and application thereof in lithium-sulfur batteries.
Background
With the continuous development of human society, the demand for energy is increasing, and traditional fossil energy is not renewable due to the fact that the fossil energy is not renewableThe defects of environmental pollution and the like can not meet the green and sustainable development concept of the current society. Therefore, development of clean and efficient energy harvesting and storage technologies is a common pursuit of all-human society. The lithium-sulfur battery has high theoretical specific capacity 1675 mAh g -1 And theoretical energy density Wh Kg -1 Is considered to be one of the most promising energy storage systems in the new generation of battery systems. Meanwhile, in the lithium sulfur battery, the sulfur anode material has the advantages of abundant reserve, low price, environmental friendliness and the like, so that the lithium sulfur battery is widely focused and researched by a plurality of students at home and abroad. However, although Li-S batteries have attractive application prospects, several problems still exist that prevent practical application of Li-S batteries:
(1) Shuttle effect: polysulfide, an intermediate product of sulfur redox reaction process, is dissolved in common ether group and other organic electrolyte, diffuses to Li metal anode under the action of concentration gradient and reacts with Li at anode + Bonding to form Li 2 S, active material loss, battery specific capacity attenuation and coulombic efficiency reduction are caused;
(2) Volume expansion: due to Li 2 S(1.66g cm −3 ) And S (2.03 g cm) −3 ) Density difference between them, so that discharge product Li 2 S, volume expansion occurs to influence the positive electrode matrix structure;
(3) The conductivity of the active material is poor: sulfur and discharge products Li 2 S/Li 2 S 2 The insulation properties of (2) lead to low active material utilization.
The water system ZIF has the advantages of simple preparation, low cost and the like. But its micrometer-scale size makes it difficult to have a high specific surface area and porosity. The monomer size of the aqueous ZIF preparation strategy at room temperature disclosed in patent CN 110876961B reaches the micron level, so that the aqueous ZIF preparation strategy is difficult to obtain a large specific surface area. This is disadvantageous for lithium sulfur battery positive electrodes requiring a high electrical contact area.
In order to overcome the problems, the nitrogen-doped porous carbon sphere with high specific surface area and porosity is obtained by regulating the water system ZIF formulation behavior at low temperature. The nitrogen doped porous carbon sphere and sulfur are compounded to provide a lithium sulfur battery positive electrode, which satisfies the characteristics of polysulfide adsorption, capacity of containing charge and discharge products, volume change, high conductivity and the like, and the lithium sulfur battery positive electrode shows excellent charge and discharge performance when being applied to a lithium sulfur battery.
Disclosure of Invention
The invention aims to provide a nitrogen-doped porous carbon sphere/S composite material, a preparation method thereof and application thereof in a lithium-sulfur battery.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the nitrogen-doped porous carbon sphere/S composite material comprises the following steps:
(1) Weighing zinc salt, adding the zinc salt into deionized water, and stirring until the zinc salt is completely dissolved to prepare solution A;
(2) Weighing 2-methylimidazole, adding into deionized water, and stirring until the solution is completely dissolved to obtain solution B;
(3) Mixing the solution A and the solution B, and uniformly stirring and reacting in a specific temperature range;
(4) Centrifugally separating the reaction solution obtained in the step (3) to obtain a solid-phase product, washing the solid-phase product with deionized water, and drying to obtain white powder;
(5) Placing the white powder obtained in the step (4) in a quartz boat, and carbonizing in a nitrogen atmosphere to obtain nitrogen-doped porous carbon spheres;
(6) Adding the obtained nitrogen-doped porous carbon spheres and sublimed sulfur into carbon disulfide solution, uniformly mixing, drying to constant weight, and carrying out heat treatment under nitrogen atmosphere to obtain the nitrogen-doped porous carbon sphere/S composite material.
Further, the concentration of zinc salt in the solution A in the step (1) is 0.002-2mol/L; the zinc salt is one or more of Zn (NO 3) 2, znSO4, (CH 3 COO) 2Zn and ZnCl 2.
Further, the concentration of 2-methylimidazole in the solution B in the step (2) is 0.05-5mol/L.
Further, the reaction temperature in the step (3) is 0-20 ℃, and the reaction time is 2-9h.
Further, the carbonization temperature in the step (5) is 700-1300 ℃, and the heating rate is 1-10 ℃/min.
Further, the temperature of the heat treatment in the step (6) was 155 ℃.
Further, in the step (6), the mass ratio of the nitrogen-doped porous carbon spheres to the sublimed sulfur is 3:7-1:9.
The second object of the invention is to disclose a lithium sulfur battery, which comprises a positive electrode and a negative electrode, wherein a diaphragm and electrode liquid are arranged between the positive electrode and the negative electrode, and the positive electrode comprises the nitrogen-doped porous carbon sphere/S composite material.
Further, the positive electrode further includes an aluminum foil.
Further, the negative electrode is lithium metal.
Further, the separator is a single-layer separator composed of polypropylene (PP).
Further, the positive electrode is a nitrogen-doped porous carbon sphere/S-aluminum foil composite positive electrode, and the preparation process comprises the following steps:
(1) Dispersing the obtained nitrogen-doped porous carbon sphere/S composite material, a conductive agent and a binder in N-methyl pyrrolidone according to a mass ratio of 8:1:1, uniformly mixing, wherein the conductive agent can be Super p Li or carbon nano tube powder, and the binder is polyvinylidene fluoride;
(2) Coating the slurry obtained in the step (1) on the surface of an aluminum foil;
(3) Drying in vacuum drying oven at 30-60deg.C for 12-36 hr.
The carbon-sulfur composite lithium-sulfur battery positive electrode material has the following advantages:
(1) The nitrogen-doped porous carbon spheres prepared by the method have rich nitrogen-doped sites and porous structures, have strong chemical and physical adsorption capacity on polysulfide, and effectively inhibit shuttle effect;
(2) The porous structure on the surface of the nitrogen-doped porous carbon sphere can buffer the volume change in the charge and discharge process;
(3) The high-temperature carbonized nitrogen-doped porous carbon sphere has excellent conductivity and has higher electric contact area with active substances, so that the polarization phenomenon in the charge and discharge process, particularly under high current density, can be effectively reduced, and the high sulfur utilization rate can be realized under high multiplying power.
Drawings
FIG. 1 is an SEM characterization of nitrogen-doped porous carbon spheres prepared according to example 1;
FIG. 2 is an SEM characterization of the nitrogen-doped porous carbon spheres prepared in example 2;
FIG. 3 is an SEM characterization of a nitrogen-doped porous nanoplatelet prepared according to comparative example 1;
FIG. 4 is an XRD pattern for example 1 and comparative example 1 without carbonization;
FIG. 5 is N of the nitrogen-doped porous carbon spheres prepared in example 1 2 Adsorption and desorption curves and pore size distribution diagrams;
FIG. 6 is N of the nitrogen-doped porous nanoplatelets prepared in comparative example 1 2 Adsorption and desorption curves and pore size distribution diagrams;
FIG. 7 is a cyclic voltammogram of lithium sulfur batteries prepared in example 1 and comparative example 1;
FIG. 8 is an electrochemical impedance spectrum of the lithium sulfur battery prepared in example 1 and comparative example 1;
fig. 9 is a cycle performance chart at 1C of the lithium sulfur battery prepared in example 1;
fig. 10 is a cycle performance chart at 1C of the lithium sulfur battery prepared in comparative example 1.
Detailed Description
The following examples are set forth in further detail to illustrate the invention, but are not intended to limit the scope thereof.
Example 1
Step 1: preparation of anode sulfur carrier nitrogen-doped porous carbon sphere of lithium sulfur battery
(1) Weighing a proper amount of zinc nitrate hexahydrate, adding the zinc nitrate hexahydrate into deionized water, and preparing a zinc nitrate aqueous solution with the concentration of 0.012 mol/L to prepare a solution A;
(2) Weighing a proper amount of 2-methylimidazole, adding the 2-methylimidazole into deionized water, and preparing a 0.12 mol/L2-methylimidazole aqueous solution to prepare a solution B;
(3) Mixing the solution A and the solution B, controlling the temperature of the reaction solution to be 10 ℃, and stirring for reaction for 3 hours;
(4) Transferring the reaction solution obtained in the step (3) into a centrifuge tube, separating a solid phase product by using a centrifuge at 7000rpm/min, washing with deionized water, and freeze-drying to obtain white powder;
(5) Placing the white powder obtained in the step (4) in a quartz boat, and carbonizing at 900 ℃ in a nitrogen atmosphere to obtain nitrogen-doped porous carbon spheres;
step 2: preparation of nitrogen-doped porous carbon sphere/S composite material
(6) Adding the obtained nitrogen-doped porous carbon spheres and sublimed sulfur into carbon disulfide solution according to the mass ratio of 2:8, uniformly mixing, drying to constant weight, and carrying out heat treatment at 155 ℃ for 12 hours in a nitrogen atmosphere to obtain the nitrogen-doped porous carbon sphere/S composite material;
step 3: preparation of nitrogen-doped porous carbon sphere/S-aluminum foil composite anode
(1) Dispersing the obtained nitrogen-doped porous carbon sphere/S composite material, a conductive agent and a binder in N-methyl pyrrolidone according to a mass ratio of 8:1:1, uniformly mixing, wherein the conductive agent can be Super p Li or carbon nano tube powder, and the binder is polyvinylidene fluoride;
(2) Coating the slurry obtained in the step (1) on the surface of an aluminum foil;
(3) Drying in vacuum drying oven at 40-60deg.C for 12-36 hr.
Step 4: lithium sulfur battery assembly
Taking the nitrogen-doped porous carbon sphere/S-aluminum foil composite anode prepared in the step 3 as an anode, taking metal lithium as a cathode, putting a commercial PP diaphragm between the anode and the cathode, putting the diaphragm into a battery shell, dripping electrolyte at two sides of the diaphragm, pressurizing and packaging to complete the assembly of the lithium-sulfur battery, wherein the electrolyte is 1M LiTFSI-DME/DOL (volume ratio of DME and DOL=1:1), and contains 1 wt% LiNO 3 。
Example 2
Step 1: preparation of anode sulfur carrier nitrogen-doped porous carbon sphere of lithium sulfur battery
(1) Weighing a proper amount of zinc nitrate hexahydrate, adding the zinc nitrate hexahydrate into deionized water, and preparing a zinc nitrate aqueous solution with the concentration of 0.012 mol/L to prepare a solution A;
(2) Weighing a proper amount of 2-methylimidazole, adding the 2-methylimidazole into deionized water, and preparing a 0.12 mol/L2-methylimidazole aqueous solution to prepare a solution B;
(3) Mixing the solution A and the solution B, controlling the temperature of the reaction solution to be 20 ℃, and stirring for reaction for 3 hours;
(4) Transferring the reaction solution obtained in the step (3) into a centrifuge tube, separating a solid phase product by using a centrifuge at 7000rpm/min, washing with deionized water, and freeze-drying to obtain white powder;
(5) Placing the white powder obtained in the step (4) in a quartz boat, and carbonizing at 900 ℃ in a nitrogen atmosphere to obtain nitrogen-doped porous carbon spheres;
step 2: preparation of nitrogen-doped porous carbon sphere/S composite material
(6) Adding the obtained nitrogen-doped porous carbon spheres and sublimed sulfur into carbon disulfide solution according to the mass ratio of 2:8, uniformly mixing, drying to constant weight, and carrying out heat treatment at 155 ℃ for 12 hours in a nitrogen atmosphere to obtain the nitrogen-doped porous carbon sphere/S composite material;
step 3: preparation of nitrogen-doped porous carbon sphere/S-aluminum foil composite anode
(1) Dispersing the obtained nitrogen-doped porous carbon sphere/S composite material, a conductive agent and a binder in N-methyl pyrrolidone according to a mass ratio of 8:1:1, uniformly mixing, wherein the conductive agent can be Super p Li or carbon nano tube powder, and the binder is polyvinylidene fluoride;
(2) Coating the slurry obtained in the step (1) on the surface of an aluminum foil;
(3) Drying in vacuum drying oven at 40-60deg.C for 12-36 hr.
Step 4: lithium sulfur battery assembly
And 3, taking the nitrogen-doped porous carbon sphere/S-aluminum foil composite anode prepared in the step 3 as an anode, taking metal lithium as a cathode, putting a commercial PP diaphragm between the anode and the cathode, putting the commercial PP diaphragm into a battery shell, dripping electrolyte at two sides of the diaphragm, pressurizing and packaging to complete the assembly of the lithium-sulfur battery, wherein the electrolyte is 1M LiTFSI-DME/DOL (volume ratio of DME and DOL=1:1), and contains 1 wt% LiNO3.
Comparative example 1
Step 1: preparation of anode sulfur carrier nitrogen-doped porous nano-sheet of lithium sulfur battery
(1) Weighing a proper amount of zinc nitrate hexahydrate, adding the zinc nitrate hexahydrate into deionized water, and preparing a zinc nitrate aqueous solution with the concentration of 0.012 mol/L to prepare a solution A;
(2) Weighing 2-methylimidazole, adding the 2-methylimidazole into deionized water, and preparing a 0.12 mol/L2-methylimidazole aqueous solution to prepare a solution B;
(3) Mixing the solution A and the solution B, controlling the temperature of the reaction solution to 25 ℃, and stirring for 3 hours;
(4) Transferring the reaction solution obtained in the step (3) into a centrifuge tube, separating a solid phase product by using a centrifuge at 7000rpm/min, washing with deionized water, and freeze-drying to obtain white powder;
(5) Placing the white powder obtained in the step (4) in a quartz boat, and carbonizing at 900 ℃ in a nitrogen atmosphere to obtain a nitrogen-doped porous nano sheet;
step 2: preparation of nitrogen-doped porous nano-sheet/S composite material
(6) Adding the obtained nitrogen-doped porous nano-sheet and sublimed sulfur into carbon disulfide solution according to the mass ratio of 2:8, uniformly mixing, drying to constant weight, and carrying out heat treatment at 155 ℃ for 12 hours in a nitrogen atmosphere to obtain the nitrogen-doped porous nano-sheet/S composite material;
step 3: preparation of nitrogen doped porous nano sheet/S-aluminum foil composite anode
(1) Dispersing the obtained ground nitrogen doped porous nano sheet/S composite material, a conductive agent and a binder in N-methyl pyrrolidone according to a mass ratio of 8:1:1, uniformly mixing, wherein the conductive agent can be Super p Li or carbon nano tube powder, and the binder is polyvinylidene fluoride;
(2) Coating the slurry obtained in the step (1) on the surface of an aluminum foil;
(3) Drying in vacuum drying oven at 30-60deg.C for 12-36 hr.
Step 4: lithium sulfur battery assembly
Taking the nitrogen-doped porous nano sheet/S-aluminum foil composite anode prepared in the step 3 as an anode, taking metal lithium as a cathode, placing a commercial PP diaphragm between the anode and the cathode, placing the commercial PP diaphragm in a battery shell, dropwise adding electrolyte at two sides of the diaphragm, pressurizing and packaging to finish the lithium-sulfur batteryCell assembly, electrolyte 1M LiTFSI-DME/DOL (volume ratio of DME to DOL=1:1), and 1 wt% LiNO 3 。
Fig. 1 and 2 are SEM images of the nitrogen-doped porous carbon spheres prepared in example 1 and example 2, from which it can be seen that the nitrogen-doped porous carbon spheres have a rough surface due to Zn volatilization during high temperature carbonization, which provides a large number of adsorption sites for polysulfide, and is advantageous for improving the cycling stability of lithium sulfur batteries. Fig. 3 is an SEM image of the nitrogen-doped porous nano-sheet prepared in comparative example 1, from which it can be seen that the nitrogen-doped porous nano-sheet is a sheet-like structure having a thickness of about 200 nm. From the characterization result of SEM, the micro morphology of the water system ZIF derivative can be effectively controlled by regulating and controlling the reaction temperature, and the small-size nano nitrogen-doped porous carbon material is obtained.
To further demonstrate the regulatory effect of reaction temperature on aqueous ZIF ligand behavior, XRD tests were performed on the uncarbonated samples of example 1 and comparative example 1. As shown in fig. 4, the two have distinct crystal structures, and the diffraction peak of comparative example 1 has extremely strong peak intensity, which indicates that comparative example 1 has excellent crystallinity and complete crystal planes. Whereas example 1 showed only one broad peak between 10-20 deg., and three characteristic peaks belonging to ZnO between 30-40 deg., the peaks were much weaker than comparative example 1 and had weaker crystallinity, and the crystal structures of the two showed a large difference. This is because, under low temperature conditions, partial crystal plane coordination of the aqueous ZIF is suppressed, resulting in incomplete coordination during the reaction. This is due to the unsaturated coordination of example 1, such that part of the crystal planes of the sample are incomplete or do not form, resulting in the formation of a spherical structure.
FIG. 5 is example 1N 2 Adsorption and desorption curves and pore size distribution diagrams, from which it can be seen that N of example 1 2 The adsorption and desorption curves are typical type IV isotherms, which are typical of N for porous carbon materials 2 Type of adsorption and desorption curve. Example 1 has a large number of microporous structures with pore diameters smaller than 1nm and also has a mesoporous structure with pore diameters of 20-30nm, which proves that example 1 has a porous structure. FIG. 6 is N of comparative example 1 2 Adsorption and desorption curves and pore size distribution diagrams, from which it can be seen that the micro-mesoporous junctions of comparative example 1The structure is significantly reduced compared to example 1. The adsorption capacity of the carrier to polysulfide can be effectively improved by more porous structures, so that the shuttle effect is inhibited.
To demonstrate the acceleration of sulfur redox kinetics by the nitrogen-doped porous carbon spheres, half cell cyclic voltammetry tests were performed on the nitrogen-doped porous carbon spheres/S, as shown in fig. 7. Compared with comparative example 1, the two reduction peaks in example 1 have higher potential and current response, which shows that the nitrogen-doped porous carbon spheres can accelerate the reaction kinetics of the sulfur reduction process, and the oxidation peaks also show higher current response, which proves that the nitrogen-doped porous carbon spheres can effectively reduce the reaction energy barrier of the sulfur oxidation reduction kinetics. To further demonstrate the effect of nitrogen-doped porous carbon spheres on the redox kinetics of sulfur, semi-cell electrochemical impedance spectroscopy tests were performed on nitrogen-doped porous carbon spheres/S, fig. 8 impedance spectroscopy consisting of charge transfer impedance (Rct) in the high frequency region and diffusion impedance, while example 1 has a smaller impedance value, demonstrating that nitrogen-doped porous carbon spheres are effective in promoting the redox kinetics of sulfur.
Fig. 9 is a long cycle performance test of example 1, and it can be seen that the battery has good cycle stability.
Fig. 10 is a long cycle performance test of the nitrogen-doped porous nano-sheet/S, and it can be seen that the cycle stability of the battery is significantly reduced compared to the nitrogen-doped porous carbon sphere/S composite positive electrode prepared in example 1.
The above is only a preferred embodiment of the present invention, and it should be noted that it should be understood by those skilled in the art that several improvements and modifications can be made without departing from the technical principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.
Claims (9)
1. The preparation method of the nitrogen-doped porous carbon sphere/S composite material is characterized by comprising the following steps of:
(1) Weighing zinc salt, adding the zinc salt into deionized water, and stirring until the zinc salt is completely dissolved to prepare solution A;
(2) Weighing 2-methylimidazole, adding into deionized water, and stirring until the solution is completely dissolved to obtain solution B;
(3) Mixing the solution A and the solution B, and uniformly stirring and reacting in a specific temperature range;
(4) Centrifugally separating the reaction solution obtained in the step (3) to obtain a solid-phase product, washing the solid-phase product with deionized water, and drying to obtain white powder;
(5) Placing the white powder obtained in the step (4) in a quartz boat, and carbonizing in a nitrogen atmosphere to obtain nitrogen-doped porous carbon spheres;
(6) Adding the obtained nitrogen-doped porous carbon spheres and sublimed sulfur into carbon disulfide solution, uniformly mixing, drying to constant weight, and performing heat treatment in nitrogen atmosphere to obtain a nitrogen-doped porous carbon sphere/S composite material;
the reaction temperature in the step (3) is 0-20 ℃, and the reaction time is 2-9h.
2. The method for preparing the nitrogen-doped porous carbon sphere/S composite material according to claim 1, wherein: the concentration of zinc salt in the solution A in the step (1) is 0.002-2mol/L; zinc salt is Zn (NO) 3 ) 2 、ZnSO 4 、(CH3COO) 2 Zn and ZnCl 2 One or more of them.
3. The method for preparing the nitrogen-doped porous carbon sphere/S composite material according to claim 1, wherein: the concentration of 2-methylimidazole in the solution B in the step (2) is 0.05-5mol/L.
4. The method for preparing the nitrogen-doped porous carbon sphere/S composite material according to claim 1, wherein: the carbonization temperature in the step (5) is 700-1300 ℃, and the heating rate is 1-10 ℃/min.
5. The method for preparing the nitrogen-doped porous carbon sphere/S composite material according to claim 1, wherein: the temperature of the heat treatment in the step (6) was 155 ℃.
6. The method for preparing the nitrogen-doped porous carbon sphere/S composite material according to claim 1, wherein: in the step (6), the mass ratio of the nitrogen-doped porous carbon spheres to the sublimated sulfur is 3:7-1:9.
7. A nitrogen-doped porous carbon sphere/S composite material made by the method of any one of claims 1-6.
8. Use of the nitrogen-doped porous carbon sphere/S composite material of claim 7 in lithium sulfur batteries.
9. The use according to claim 8, characterized in that: the nitrogen-doped porous carbon sphere/S composite material is used for preparing a lithium sulfur battery positive electrode, and the preparation method comprises the following steps:
1) Dispersing the nitrogen-doped porous carbon sphere/S composite material, the conductive agent and the binder in N-methyl pyrrolidone according to a mass ratio of 8:1:1, and uniformly mixing to obtain slurry;
2) Coating the slurry obtained in the step 1) on the surface of an aluminum foil;
3) And (3) drying in a vacuum drying oven at 30-60 ℃ for 12-36 hours to obtain the nitrogen doped porous carbon sphere/S-aluminum foil composite anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210567983.1A CN114751395B (en) | 2022-05-24 | 2022-05-24 | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210567983.1A CN114751395B (en) | 2022-05-24 | 2022-05-24 | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114751395A CN114751395A (en) | 2022-07-15 |
| CN114751395B true CN114751395B (en) | 2023-07-21 |
Family
ID=82335143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210567983.1A Active CN114751395B (en) | 2022-05-24 | 2022-05-24 | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114751395B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115377607A (en) * | 2022-09-01 | 2022-11-22 | 陕西科技大学 | BC load MOFs derived CNF/Co-Co x S y -NC composite material and preparation and application method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409733A (en) * | 2014-12-24 | 2015-03-11 | 华南师范大学 | Nitrogen doped porous carbon/sulfur composite positive material as well as preparation method and application thereof |
| CN110336032A (en) * | 2019-07-10 | 2019-10-15 | 中国人民解放军国防科技大学 | Preparation method of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon and application of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon in lithium-sulfur battery |
| CN112062229A (en) * | 2020-08-12 | 2020-12-11 | 浙江工业大学 | Bi/MOF-derived porous carbon sphere composite material and preparation method and application thereof |
| CN112661137A (en) * | 2020-12-24 | 2021-04-16 | 南京航空航天大学 | Porous carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery |
-
2022
- 2022-05-24 CN CN202210567983.1A patent/CN114751395B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409733A (en) * | 2014-12-24 | 2015-03-11 | 华南师范大学 | Nitrogen doped porous carbon/sulfur composite positive material as well as preparation method and application thereof |
| CN110336032A (en) * | 2019-07-10 | 2019-10-15 | 中国人民解放军国防科技大学 | Preparation method of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon and application of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon in lithium-sulfur battery |
| CN112062229A (en) * | 2020-08-12 | 2020-12-11 | 浙江工业大学 | Bi/MOF-derived porous carbon sphere composite material and preparation method and application thereof |
| CN112661137A (en) * | 2020-12-24 | 2021-04-16 | 南京航空航天大学 | Porous carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery |
Non-Patent Citations (2)
| Title |
|---|
| hierarchically porous multilayered carbon barriers for high-performance Li-S batteries;zhi chang;《chemisty A European Journal》;3768-3775 * |
| 基于分子设计多孔碳球的制备研究进展;吕路路;龙剑平;朱朋莉;;电子元件与材料(第03期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114751395A (en) | 2022-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110104630B (en) | Porous carbon composite material for battery diaphragm and preparation method and application thereof | |
| CN108565446B (en) | Preparation method of porous nitrogen-doped carbon-coated graphite material | |
| CN108878877B (en) | Positive electrode active material for aqueous zinc ion secondary battery and aqueous zinc ion secondary battery | |
| CN108963235B (en) | Graphene-enhanced carbon-coated titanium manganese phosphate sodium microsphere electrode material and preparation method and application thereof | |
| CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
| CN108598394B (en) | Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof | |
| CN112038635B (en) | Lithium-sulfur battery graphene-loaded cementite particle composite positive electrode material and preparation method thereof | |
| CN110611084B (en) | Lithium-sulfur secondary battery with long cycle life and 100% coulombic efficiency | |
| CN111313111A (en) | Heteroatom-doped carbon/CoS based on metal organic framework derivation2Functional material and application thereof | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN113571841B (en) | Lithium-sulfur battery composite diaphragm and preparation method thereof | |
| CN114751395B (en) | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery | |
| CN111370699A (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN113943016A (en) | Binary transition metal sulfide material and application thereof | |
| CN111261870B (en) | NASICON structure Na4CrMn(PO4)3Method for producing materials and use thereof | |
| Zhang et al. | Preparation and optimization of nanoporous hollow carbon spheres/S composite cathode materials for Li-S battery | |
| CN110783542A (en) | Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery | |
| CN110021748A (en) | A kind of lithium-sulfur cell Heteroatom doping porous carbon positive electrode and preparation method thereof | |
| Wang et al. | A functional TiO2-coated separator for high-performance Li-S batteries | |
| CN112599754B (en) | Polymer modified composite positive electrode for lithium-sulfur battery and preparation method thereof | |
| CN114220971A (en) | Three-dimensional ordered cobalt-nitrogen microporous carbon material with strong catalytic action and preparation method and application thereof | |
| CN110828810B (en) | Iron-doped porous carbon-sulfur material based on polypyrrole and preparation method and application thereof | |
| CN110416512B (en) | Based on Bi4Ti3O12Preparation method of @ C/S composite material, composite material and application | |
| CN115050938B (en) | Preparation method of heteroatom doped hollow carbon material and application of heteroatom doped hollow carbon material in lithium sulfur battery | |
| CN112110488B (en) | Metal sulfide and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |