CN115050938A - Preparation method of heteroatom-doped hollow carbon material and application of heteroatom-doped hollow carbon material in lithium-sulfur battery - Google Patents
Preparation method of heteroatom-doped hollow carbon material and application of heteroatom-doped hollow carbon material in lithium-sulfur battery Download PDFInfo
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- CN115050938A CN115050938A CN202210690506.4A CN202210690506A CN115050938A CN 115050938 A CN115050938 A CN 115050938A CN 202210690506 A CN202210690506 A CN 202210690506A CN 115050938 A CN115050938 A CN 115050938A
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a heteroatom-doped hollow carbon material and application of the heteroatom-doped hollow carbon material in a lithium-sulfur battery, which comprises the following steps: mixing the aqueous metal salt solution with the aqueous organic ligand solution, and adding a chelating agent as a competitive ligand; separating the solid phase product, and drying to obtain white powder; and carbonizing the dried sample to obtain the heteroatom-doped hollow carbon material. The method has simple process and low production cost, and the prepared heteroatom-doped hollow carbon material has a hollow structure with an adjustable shell layer (2-100nm) and can provide a large specific surface area, so that the electric contact area of a carrier is increased, the electron transmission of a positive electrode is promoted, and the redox kinetics of sulfur species is accelerated; at the same time, a holding space is provided for sulfur species, and the volume expansion and shuttle effect are relieved. In addition, the hetero atom doping enhances the interaction between the carbon material and polysulfide, reduces the polysulfide conversion energy barrier, and further improves the redox kinetics of the battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a simple preparation method of a heteroatom-doped hollow carbon material and application of the heteroatom-doped hollow carbon material in a lithium-sulfur battery.
Background
With the rapid development of society, the release of greenhouse gases in all countries in the world is increased year by year, which causes global climate change, and the climate change seriously threatens the survival of human beings and the sustainable development of society. In order to actively deal with the problem, the renewable clean energy is required to be fully developed and utilized. However, clean energy sources such as wind energy and solar energy have a common problem that the energy space-time distribution is not uniform, and the requirement of continuous power supply of a power grid cannot be met. In order to solve the problem, a matched energy storage power station must be established, so that redundant electric energy is stored in a battery pack at the rich stage of wind energy and the like, and the power supply requirement of a power grid is balanced. Among the numerous energy storage systems, have a high theoretical specific capacity (1675 mAh g) -1 ) Energy density (2600 Wh kg) -1 ) Lithium sulfur batteries with the advantages of wide raw material sources, low cost, environmental friendliness and the like are considered to be powerful candidates for next-generation energy storage systems. However, practical application of lithium-sulfur batteries is severely limited due to problems of charge and discharge product insulation, "shuttle effect", slow redox kinetics of sulfur species, and the like.
In order to overcome the problems, the carbon-sulfur composite anode can be constructed by compounding a carbon carrier with good conductivity and sulfur, so that the charge transmission efficiency of the sulfur anode can be improved, and the problem of the insulativity of a charge-discharge product is solved. However, the conventional solid carbon material has a carbon structure inside which is difficult to contact with sulfur species to form an interface for charge transfer, which affects further improvement of charge transfer efficiency of the positive electrode interface. And hollow structure, because its abundant inner space, big specific surface area, can not only effectively improve carrier and sulphur electric contact area to promote anodal charge transmission efficiency, still provide higher accommodation space for sulphur species, restrain polysulfide diffusion, improved anodal structure and electrochemical stability in the cyclic process. In addition, in order to solve the problem that the adsorption capacity of the carbon material to polysulfide is weak, the electronic structure of the carbon network is adjusted through a heteroatom doping strategy, so that the adsorption of a carrier to polysulfide is favorably improved, and polysulfide conversion is promoted.
Patent CN 112168983B discloses a hollow carbon nanocomposite and a preparation method thereof, which utilizes phenolic Resin (RF) as a shell precursor and silicon dioxide (SiO) 2 ) The nano particles are used as a core template to obtain SiO taking silicon oxide as a core and phenolic resin as a shell 2 @ RF core-shell nano-spherical particles. Roasting for a period of time at a certain temperature to obtain the core-shell type nano composite material taking silicon oxide as a core and carbon material as a shell. And finally, selectively etching to remove the silicon oxide core to obtain the hollow carbon nano composite material. Although the method can prepare the hollow carbon material, the complicated preparation process of the template method and a large amount of waste liquid generated in the preparation process make the mass production difficult.
Patent CN 110371950 a discloses a method for preparing a hollow carbon material, which uses bacteria as a template, then coats a polymer on cell walls under stirring conditions, and finally obtains the hollow carbon material by calcining. The method simplifies the template removal post-treatment step, but the method still needs bacteria as templates, so that the production process is complicated and the cost is increased.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention provides a simple method for preparing a heteroatom-doped hollow carbon material, wherein the coordination behavior of an MOF material is regulated by introducing a competitive ligand (chelating agent), and the chelating agent can compete with the metal ion in the coordination process of an organic ligand of the MOF and the metal ion due to the strong chelating effect of the chelating agent on the metal ion, so that part of the organic ligand sites are replaced by chelating agent molecules, the coordination of part of crystal faces of the MOF is hindered to form a hollow structure, the hollow-structure MOF material is prepared in one step, and finally the heteroatom-doped hollow carbon material is obtained through carbonization. The method has the advantages of simple process and low production cost, and the prepared heteroatom-doped hollow carbon material has adjustable shell thickness (2-100nm) and high conductivity by controlling the addition of the competitive ligand, has good adsorption effect on polysulfide, can accommodate volume change of charge and discharge products and promote sulfur species redox kinetics, can greatly improve the cycle stability, rate capability and coulombic efficiency of the lithium-sulfur battery anode by applying the heteroatom-doped hollow carbon material to the lithium-sulfur battery anode, and has higher practical application value.
The first purpose of the invention is to disclose a simple preparation method of a heteroatom-doped hollow carbon material, which comprises the following steps:
(1) weighing metal salt, adding the metal salt into a solvent, and stirring until the metal salt is completely dissolved to prepare a solution A;
(2) weighing organic ligand, adding the organic ligand into a solvent, and stirring until the organic ligand is completely dissolved to prepare a solution B;
(3) mixing the solution A and the solution B, and stirring for reaction for 30 min;
(4) immediately dripping a chelating agent with a certain proportion into the mixed solution obtained in the step (3) to participate in competitive coordination, and continuously stirring and reacting for a period of time;
(5) after stirring is stopped, standing for a period of time for aging treatment to promote the formation of a hollow structure;
(6) separating a solid-phase product from the reaction solution obtained in the step (5), washing with deionized water, and drying to obtain white powder;
(7) and (4) putting the white powder obtained in the step (6) into a quartz boat, and carbonizing the white powder in a nitrogen atmosphere within a specific temperature range to obtain the heteroatom-doped hollow carbon.
Preferably, in the step (1), the concentration of the metal salt in the solution A is 0.005-2 mol/L.
Preferably, in step (1), in the solution a, the metal salt includes but is not limited to: nitrate, chloride, sulfate and acetate of iron, cobalt, nickel, zinc, copper and zirconium.
Preferably, in the step (2), the concentration of the organic ligand in the solution B is 0.05-5mol/L, and the molar ratio of the organic ligand to the metal salt is 2:1-20: 1.
Preferably, in step (2), in the solution B, the organic ligands include, but are not limited to: one or more of 2-methylimidazole, terephthalic acid, trimesic acid and 2-aminoterephthalic acid.
Preferably, in step (1) and step (2), the solvent includes, but is not limited to: one or more of deionized water, methanol, ethanol, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide and 1-chloro-1-phenylethane.
Preferably, in step (4), the chelating agent includes, but is not limited to: one or more of phytic acid, nitrilotriacetic acid, ethylene diamine tetraacetic acid, dithizone, 8-hydroxyquinoline, phenanthroline, potassium sodium tartrate, ammonium citrate, ethylenediamine, 2' -bipyridine, 1, 10-diazobenzene, oxalic acid and tannic acid.
Preferably, in step (4), the ratio of the addition of the competing ligand chelator is: 1wt% -80wt% of the mass of the metal salt.
Preferably, in step (4), the reaction time is 2 to 12 hours.
Preferably, in step (5), the aging time is from 1 to 24 hours.
Preferably, in the step (7), the carbonization temperature is 700-.
The second purpose of the invention is to disclose a lithium-sulfur battery positive electrode material, which is prepared by the method comprising the following steps: adding the heteroatom-doped hollow carbon material and sublimed sulfur into a carbon disulfide solution, uniformly mixing, drying to constant weight, and carrying out heat treatment in a nitrogen atmosphere to obtain the heteroatom-doped hollow carbon/sulfur composite material.
Preferably, the heteroatom-doped hollow carbon/sulfur composite material has a heat treatment temperature of 155 ℃.
Preferably, the heteroatom-doped hollow carbon/sulfur composite material has a mass ratio of the heteroatom-doped hollow carbon material to sublimed sulfur of 3:7-1: 9.
The third purpose of the invention is to disclose a lithium-sulfur battery, which comprises a positive electrode and a negative electrode, wherein a diaphragm and an electrode solution are arranged between the positive electrode and the negative electrode, and the positive electrode comprises the heteroatom-doped hollow carbon/sulfur composite material.
Preferably, the positive electrode further includes an aluminum foil.
Preferably, the negative electrode is metallic lithium.
Preferably, the separator is a single layer separator composed of polypropylene (PP).
Preferably, the positive electrode is a heteroatom-doped hollow carbon/sulfur composite-aluminum foil composite positive electrode.
The preparation process comprises the following steps:
(1) dispersing the obtained heteroatom-doped hollow carbon/sulfur composite material, a conductive agent and a binder in N-methylpyrrolidone according to the mass ratio of 8:1:1, uniformly mixing, wherein the conductive agent can be one or more of Super p Li or carbon nanotube 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 a vacuum drying oven at 30-60 deg.C for 12-36 hr.
The heteroatom-doped hollow carbon/sulfur composite lithium-sulfur battery positive electrode material has the following advantages:
(1) the heteroatom-doped hollow carbon material prepared by the invention has a very large specific surface area, so that on one hand, the electrical contact area of a carrier and sulfur is effectively increased, and the charge transmission efficiency of a positive electrode is improved; on the other hand, a containing space can be provided for sulfur species, polysulfide diffusion is limited, the damage of the anode structure caused by volume expansion of a discharge product is avoided, and the stability of the anode structure is improved;
(2) the heteroatom (N, P, S) doping strategy of the heteroatom-doped hollow carbon material adjusts the electronic structure of a carbon network, improves the affinity of the carbon material for polysulfide, reduces the polysulfide conversion energy barrier, and improves the redox kinetics of the battery;
(3) by the aid of the advantages, the heteroatom-doped hollow carbon/sulfur composite positive electrode prepared by taking the heteroatom-doped hollow carbon material as the matrix can greatly improve the cycle stability, rate capability and coulombic efficiency of the lithium-sulfur battery positive electrode, and has high practical application value.
Drawings
FIG. 1 is a TEM representation of example 1;
FIG. 2 is a TEM representation of example 2;
FIG. 3 is a SEM representation of comparative example 1;
FIG. 4 is an embodiment1. N of example 2 and comparative example 1 2 Adsorption and desorption curves;
FIG. 5 is a plot of the pore size distribution for example 1, example 2, and comparative example 1;
FIG. 6 is a cyclic voltammogram of the lithium sulfur batteries of example 1, example 2, and comparative example 1;
FIG. 7 is electrochemical impedance spectra of lithium sulfur batteries of example 1, example 2, and comparative example 1;
fig. 8 is a graph of rate performance of the lithium sulfur batteries of example 1, example 2 and comparative example 1;
FIG. 9 is a graph of long cycle performance at 1C for the lithium sulfur cells of example 1, example 2, and comparative example 1;
FIG. 10 is XPS survey spectra of example 1, example 2 and comparative example 1.
Detailed Description
The following examples are given to illustrate the present invention but not to limit the scope of the present invention.
Example 1
Step 1: preparation of hetero-atom doped hollow carbon material of lithium-sulfur battery anode sulfur carrier
(1) Weighing 1.32g of zinc nitrate hexahydrate, adding the mixture into 360ml of deionized water, and preparing 0.012 mol/L of zinc nitrate aqueous solution to obtain solution A;
(2) weighing 3.94g of 2-methylimidazole, adding into 360ml of deionized water, and preparing 0.12 mol/L2-methylimidazole water solution to obtain a solution B;
(3) mixing the solution A and the solution B, and stirring for reaction for 30 min;
(4) immediately dripping 150 uL of 70wt% phytic acid aqueous solution into the mixed solution obtained in the step (3), and continuously reacting for 3 h;
(5) after stirring is stopped, standing for 8 hours for aging treatment to promote the formation of a hollow structure;
(6) transferring the reaction solution obtained in the step (5) into a centrifuge tube, separating a solid-phase product by using a centrifuge at 7000rpm/min, washing with deionized water, and drying to obtain white powder;
(7) and (3) placing the white powder obtained in the step (6) in a quartz boat, carbonizing the white powder at 900 ℃ for 2 hours in a nitrogen atmosphere to obtain the P-doped hollow carbon material (shown in the figure 1 and the figure 10) with the P doping amount of 1.01 percent and the N doping amount of 4.03 percent and the diameter of about 60nm, and characterizing the doping type and the doping amount of the heteroatom by XPS.
Step 2: preparation of heteroatom doped hollow carbon/sulfur composite material
Adding the obtained heteroatom-doped hollow carbon material and sublimed sulfur into a 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 heteroatom-doped hollow carbon/sulfur composite material.
And 3, step 3: preparation of heteroatom-doped hollow carbon/sulfur-aluminum foil composite positive electrode
(1) Dispersing the obtained heteroatom-doped hollow carbon/sulfur composite material, a conductive agent and a binder in N-methylpyrrolidone according to the mass ratio of 8:1:1, and uniformly mixing, wherein the conductive agent is carbon nanotube 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 a vacuum drying oven at 40 deg.C for 12 hr.
And 4, step 4: lithium sulfur battery assembly
And 3, taking the heteroatom-doped hollow carbon/sulfur-aluminum foil composite positive electrode prepared in the step 3 as a positive electrode and metal lithium as a negative electrode, placing a commercial PP diaphragm between the positive electrode and the negative electrode, placing the diaphragm in a battery shell, dropwise adding electrolyte on two sides of the diaphragm, and pressurizing and packaging to complete the assembly of the lithium-sulfur battery, wherein the electrolyte is 1M LiTFSI-DME/DOL (volume ratio of DME to DOL = 1: 1) and contains 1wt% of LiNO 3 。
Example 2
Step 1: preparation of hetero-atom doped hollow carbon material of sulfur carrier of positive electrode of lithium-sulfur battery
(1) Weighing 1.32g of zinc nitrate hexahydrate, adding the mixture into 360ml of deionized water, and preparing 0.012 mol/L of zinc nitrate aqueous solution to obtain solution A;
(2) weighing 3.94g of 2-methylimidazole, adding into 360ml of deionized water, and preparing 0.12 mol/L2-methylimidazole water solution to obtain a solution B;
(3) mixing the solution A and the solution B, and stirring for reaction for 30 min;
(4) immediately dropwise adding 300 uL of 70wt% phytic acid aqueous solution into the mixed solution obtained in the step (3), and continuously reacting for 3 hours;
(5) after stirring is stopped, standing for 8 hours for aging treatment to promote the formation of a hollow structure;
(6) transferring the reaction solution obtained in the step (5) into a centrifuge tube, separating a solid-phase product by using a centrifuge at 7000rpm/min, washing with deionized water, and drying to obtain white powder;
(7) and (3) putting the white powder obtained in the step (6) into a quartz boat, and carbonizing the white powder at 900 ℃ for 2 hours in a nitrogen atmosphere to obtain the P and N doped hollow carbon material with the P doping amount of 1.93 percent and the N doping amount of 2.95 percent and the diameter of about 60nm (shown in the figure 2 and the figure 10).
Step 2: preparation of heteroatom doped hollow carbon/sulfur composite material
Adding the obtained heteroatom-doped hollow carbon material and sublimed sulfur into a 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 heteroatom-doped hollow carbon/sulfur composite material.
And step 3: preparation of heteroatom-doped hollow carbon/sulfur-aluminum foil composite anode
(1) Dispersing the obtained heteroatom doped hollow carbon/sulfur composite material, a conductive agent and a binder in a mass ratio of 8:1:1 in N-methylpyrrolidone, and uniformly mixing, wherein the conductive agent is carbon nanotube 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 a vacuum drying oven at 40 deg.C for 12 hr.
And 4, step 4: lithium sulfur battery assembly
And 3, taking the heteroatom-doped hollow carbon/sulfur-aluminum foil composite positive electrode prepared in the step 3 as a positive electrode and metal lithium as a negative electrode, placing a commercial PP diaphragm between the positive electrode and the negative electrode, placing the diaphragm in a battery shell, dropwise adding electrolyte on two sides of the diaphragm, and pressurizing and packaging to complete the assembly of the lithium-sulfur battery, wherein the electrolyte is 1M LiTFSI-DME/DOL (volume ratio of DME to DOL = 1: 1) and contains 1wt% of LiNO 3 。
Comparative example 1
Step 1: preparation of positive electrode sulfur carrier nitrogen-doped porous carbon sphere of lithium-sulfur battery
(1) Weighing 1.32g of zinc nitrate hexahydrate, adding the mixture into 360ml of deionized water, and preparing 0.012 mol/L of zinc nitrate aqueous solution to obtain solution A;
(2) weighing 3.94g of 2-methylimidazole, adding into 360ml of deionized water, and preparing 0.12 mol/L2-methylimidazole water solution to obtain a solution B;
(3) mixing the solution A and the solution B, controlling the temperature of the reaction solution to be 15 ℃, 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 drying to obtain white powder;
(5) and (5) putting the white powder obtained in the step (4) into a quartz boat, and carbonizing at 1000 ℃ for 2 hours under a nitrogen atmosphere to obtain 60nm nitrogen-doped porous carbon spheres with the N doping amount of 5.46% (shown in figures 3 and 10).
And 2, step: preparation of nitrogen-doped porous carbon sphere/sulfur composite material
Adding the obtained nitrogen-doped porous carbon spheres and sublimed sulfur into a 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/sulfur composite material;
and step 3: preparation of nitrogen-doped porous carbon sphere/sulfur-aluminum foil composite positive electrode
(1) Dispersing the obtained nitrogen-doped porous carbon sphere/sulfur composite material, a conductive agent and a binder in N-methyl pyrrolidone according to the mass ratio of 8:1:1, and uniformly mixing, wherein the conductive agent is 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 a vacuum drying oven at 40 deg.C for 12 hr.
And 4, step 4: lithium sulfur battery assembly
Taking the nitrogen-doped porous carbon sphere/sulfur-aluminum foil composite positive electrode prepared in the step 3 as a positive electrode and metal lithium as a negative electrode, placing a commercial PP diaphragm between the positive electrode and the negative electrode, placing the diaphragm in a battery shell, dropwise adding electrolyte on two sides of the diaphragm, and pressurizing and packagingAnd completing the assembly of the lithium-sulfur battery, wherein the electrolyte is 1M LiTFSI-DME/DOL (the volume ratio of DME to DOL is = 1: 1) and contains 1wt% LiNO 3 。
FIG. 1 is a TEM image of the heteroatom-doped hollow carbon material prepared in example 1, from which the hollow structure of the heteroatom-doped hollow carbon material can be clearly observed, and the spherical shell thickness of example 1 is about 8 nm; meanwhile, the shell layer thickness is continuously reduced along with the increase of the addition amount of the phytic acid, and the spherical shell thickness of the embodiment 2 is only 5 nm (shown in figure 2), which shows that the microstructure of the MOF material can be effectively adjusted by utilizing a competitive coordination mechanism of a chelating agent and dimethyl imidazole. The formation of the hollow structure is beneficial to improving the electric contact area of the carrier and the sulfur, so that the charge transmission efficiency of the battery anode interface is greatly improved, and the promotion effect on improving the reaction kinetics of sulfur species and improving the utilization rate of the anode active substance is achieved. And the hollow internal structure also provides a larger accommodating space for sulfur species, and the buffer composite positive electrode causes structural damage due to volume expansion of the sulfur species in the circulation process.
FIG. 4 and the drawing N 2 Adsorption-desorption curves and pore size distribution profiles, as can be seen from fig. 4, the isotherms of example 1, example 2 and comparative example 1 are typical type iv isotherms, and the adsorption amount of the adsorption-desorption curves in the low relative pressure region (P/Po =0) rises sharply almost vertically upward, which further demonstrates that the microporous structure exists in all of example 1, example 2 and comparative example 1. In the high relative pressure region (P/Po =0.8-0.95), the hysteresis loops of example 1, example 2 and comparative example 1 are obviously different, which may be caused by the isothermal curve change due to the hollow structure inside example 1 and example 2. For further analysis of the pore structure composition of the samples, the pore size distribution curves of examples 1, 2 and comparative example 1 are shown in fig. 5, and the peak intensity of the sample micropores sharply increases with the addition of phytic acid, which is mainly due to the formation of hollow structures, sufficiently exposing the microporous structure originally buried inside. However, as the amount of phytic acid added continues to increase, the peak intensity of the micropores of example 2 decreases because the thickness of the spherical shell of the sample further decreases, and the excessively thin spherical shell decreases the content of the microporous structure. High specific surface area for lithium sulfurThe electrochemical performance of the battery has an accelerating effect, and the specific surface areas of the example 1, the example 2 and the comparative example 1 are 1637 m respectively according to the low-temperature nitrogen adsorption-desorption test result 2 g -1 And 1584.5 m 2 g -1 、964.7 m 2 g -1 . Compared with comparative example 1, the specific surface area of example 1 and example 2 is significantly increased due to the formation of the hollow structure, which greatly increases the electrical contact area of the carrier and shortens the charge transfer distance of the interface of the positive electrode.
Fig. 6 is a graph showing the accelerating effect of the heteroatom-doped hollow carbon material on sulfur redox kinetics, and a half-cell Cyclic Voltammetry (CV) test is performed, so that the CV curves Pc1 and Pc2 of example 1 and example 2 have significantly increased reduction peak current densities compared with comparative example 1, and the kinetics of the hollow structure are improved in the sulfur species reduction reaction stage. Further, as can be seen from the oxidation peak (Pa) of the CV curve of the half cell, the oxidation peaks of examples 1 and 2 not only had higher peak current densities than comparative example 1, but also the oxidation peak was split from a single peak to a double peak, demonstrating that the heteroatom-doped hollow carbon material contributes to the reduction of Li 2 And S is an oxidation energy barrier, so that the polarization of the battery is reduced, and the oxidation kinetics of sulfur species are promoted to be improved.
To further demonstrate the effect of the heteroatom-doped hollow carbon material on sulfur redox kinetics, half-cell electrochemical impedance spectroscopy tests were performed on the heteroatom-doped hollow carbon/sulfur composite material, and fig. 7 impedance spectroscopy consisted of charge transfer impedance (Rct) and diffusion impedance in the high-frequency region, while example 1(29.0 Ω) and example 2(53.8 Ω) had smaller impedance values than comparative example 1(90.9 Ω), and also demonstrated that the heteroatom-doped hollow carbon material was effective in promoting the redox kinetics of sulfur species.
Fig. 8 is a rate capability test. As can be seen, the capacities of example 1, example 2 and comparative example 1 were 1386 mAh g, respectively, at a low current density of 0.1C -1 、1377 mAh g -1 And 1309.1 mAh g -1 . The capacity of comparative example 1 decayed rapidly with increasing current density, giving only 409.6 mAh g at a high current density of 3C -1 And capacity fading of example 1 and example 2Smaller, still maintain 644.6 mAh g -1 And 591.8 mAh g -1 The discharge capacity of (2) shows more excellent rate capability.
FIG. 9 is a long cycle performance test at 1C current density. It can be seen that after 500 cycles, example 1, example 2 and comparative example 1 maintained 504.5 mAh g, respectively -1 、488.5 mAh g -1 And 441 mAh g -1 The reversible capacity and sulfur utilization rate of (2) are respectively maintained at 30.1%, 29.2% and 26.3%. Example 1 and example 2 still maintain higher active utilization than comparative example 1.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a heteroatom-doped hollow carbon material is characterized by comprising the following steps:
(1) weighing metal salt, adding the metal salt into a solvent, and stirring until the metal salt is completely dissolved to prepare a solution A;
(2) weighing organic ligand, adding the organic ligand into a solvent, and stirring until the organic ligand is completely dissolved to prepare a solution B;
(3) mixing the solution A and the solution B, and stirring for reaction for 30 min;
(4) immediately dripping a chelating agent with a certain proportion into the mixed solution obtained in the step (3) to participate in competitive coordination, and continuously stirring and reacting for a period of time;
(5) after stirring is stopped, standing for a period of time for aging treatment to promote the formation of a hollow structure;
(6) separating a solid-phase product from the reaction solution obtained in the step (5), washing with deionized water, and drying to obtain white powder;
(7) and (4) putting the white powder obtained in the step (6) into a quartz boat, and carbonizing the white powder in a nitrogen atmosphere within a specific temperature range to obtain the heteroatom-doped hollow carbon.
2. The method of claim 1, wherein: in the step (1), the concentration of the metal salt in the solution A is 0.005-2 mol/L.
3. The method of claim 1, wherein: in the step (1), the metal salt includes: nitrate, chloride, sulfate and acetate of iron, cobalt, nickel, zinc, copper and zirconium.
4. The production method according to claim 1, characterized in that: in the step (2), the concentration of the organic ligand in the solution B is 0.05-5mol/L, and the molar ratio of the organic ligand to the metal salt is 2:1-20: 1.
5. The method of claim 1, wherein: in the step (2), the organic ligand includes: one or more of 2-methylimidazole, terephthalic acid, trimesic acid and 2-aminoterephthalic acid.
6. The production method according to claim 1, characterized in that: in the step (1) and the step (2), the solvent includes: one or more of deionized water, methanol, ethanol, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide and 1-chloro-1-phenylethane.
7. The method of claim 1, wherein: in the step (4), the chelating agent includes: one or more of phytic acid, nitrilotriacetic acid, ethylene diamine tetraacetic acid, dithizone, 8-hydroxyquinoline, phenanthroline, potassium sodium tartrate, ammonium citrate, ethylenediamine, 2' -bipyridyl, 1, 10-diazobenzene, oxalic acid and tannic acid; the addition proportion of the chelating agent is 1wt% -80wt% of the mass of the metal salt.
8. The method of claim 1, wherein: in the step (4), the reaction time is 2-12 h; in the step (5), the aging time is 1-24 h; in the step (7), the carbonization temperature is 700-.
9. Use of the heteroatom-doped hollow carbon material prepared by the preparation method according to any one of claims 1 to 8 in a lithium-sulfur battery.
10. The method for preparing the lithium-sulfur battery cathode material according to claim 9, wherein the heteroatom-doped hollow carbon material is used for preparing the lithium-sulfur battery cathode material, and comprises the following steps: adding the heteroatom-doped hollow carbon material and sublimed sulfur into a carbon disulfide solution, uniformly mixing, drying to constant weight, and carrying out heat treatment in a nitrogen atmosphere to obtain a heteroatom-doped hollow carbon/sulfur composite material; wherein the heat treatment temperature is 155 ℃, and the mass ratio of the heteroatom-doped hollow carbon material to the sublimed sulfur is 3:7-1: 9.
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