CN111082015A - Cobalt disulfide/carbon nanofiber/sulfur composite material, and preparation method and application thereof - Google Patents
Cobalt disulfide/carbon nanofiber/sulfur composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a cobalt disulfide/carbon nanofiber/sulfur composite material, which consists of carbon nanofibers, cobalt disulfide nanoparticles and sulfur; the surface of the carbon nanofiber is compounded with cobalt disulfide nanoparticles which are closely and orderly arranged, and the carbon nanofiber and the cobalt disulfide nanoparticles form a corn rod-shaped structure; the sulfur is supported in the corn cob structure. The application also provides a preparation method and application of the composite material. The cobalt disulfide/carbon nanofiber/sulfur composite material provided by the application has a unique corn-shaped nanostructure, so that the composite material has chemical adsorption and redox catalysis capabilities, is directly applied to a lithium-sulfur battery, and provides high specific mass capacity and long cycle performance in charge-discharge cycles.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a cobalt disulfide/carbon nanofiber/sulfur composite material, and a preparation method and application thereof.
Background
The lithium-sulfur battery takes sulfur as a positive pole reactant and lithium as a negative pole; during discharging, the negative electrode reacts to enable lithium to lose electrons and become lithium ions, the positive electrode reacts to enable sulfur, the lithium ions and the electrons to react to generate sulfide, and the potential difference between the positive electrode and the negative electrode is the discharging voltage provided by the lithium-sulfur battery; under the action of an applied voltage, the reaction of the positive electrode and the negative electrode of the lithium-sulfur battery is carried out reversely, namely, the charging process is carried out. Elemental sulfur is completely changed into S according to unit mass2-The theoretical specific discharge capacity of sulfur obtained from the provided electric quantity is 1675mAh/g, and the theoretical specific discharge capacity of elemental lithium obtained from the same method is 3860 mAh/g; the theoretical discharge voltage of a lithium-sulfur battery is 2.287V, and lithium sulfide (Li) is generated when sulfur and lithium are completely reacted2S), the theoretical specific energy of discharge mass of the corresponding lithium-sulfur battery is 2600Wh/kg, which is 10 times of the specific energy of 220Wh/kg of the currently mainstream ternary lithium battery. In addition, the lithium-sulfur battery adopts elemental sulfur as a positive electrode material, so that the cost is low, and the lithium-sulfur battery has a great market prospect.
However, there are still many problems that prevent the large-scale application of lithium sulfur batteries, and there are two main technical problems: 1) elemental sulfur has poor electronic and ionic conductivity, and sulfur materials have very low conductivity at room temperature (5.0X 10)-30S·cm-1) End product of the reaction Li2S2And Li2S is also an electronic insulator, which is not conducive to high rate performance of the battery; 2) the intermediate discharge product of the lithium-sulfur battery can be dissolved in the organic electrolyte, the viscosity of the electrolyte is increased, the ionic conductivity is reduced, polysulfide ions can migrate between a positive electrode and a negative electrode, active substance loss and electric energy waste are caused, and the dissolved polysulfide can cross a diaphragm to diffuse to the negative electrode to react with the negative electrode, so that a solid electrolyte interface film (SEI film) of the negative electrode is damaged.
In order to improve the two outstanding problems of shuttle effect of lithium sulfur batteries and polysulfides and low reactivity of short-chain polysulfides, a great deal of research has been carried out by researchers. Cobalt sulfide is a unique transition metal sulfide, has a cubic crystal form and excellent metal conductivity, and is widely applied to supercapacitors, catalytic materials for hydrogen evolution reaction and oxygen evolution reaction, and negative electrode materials of lithium ion batteries. But there is little research related to the application of cobalt disulfide to the dual-functionalization design of catalysis and chemisorption of lithium sulfur battery cathode materials.
In the Journal of Power Sources 325(2016) (71-78) of the English literature, the authors report a cobalt disulfide/carbon paper composite for use as a chemisorbent for polysulfides in lithium sulfur battery anodes. The author firstly chemically deposits cobalt hydroxide on the surface of carbon paper, then carries out high-temperature vulcanization to obtain a cobalt disulfide/carbon paper composite material, and then melts and permeates sulfur into the composite material to finally obtain the cobalt disulfide/carbon paper/sulfur composite cathode material. The material shows good electrochemical performance when being used for the anode of a lithium-sulfur battery. Under the condition of low-current 0.2C charging and discharging, the capacity of the first circle of the battery reaches 1200mAh/g, and after the first circle of the battery is circulated to 200 circles, the capacity is reduced to 800 mAh/g. However, when the current is increased to 0.5C, the capacity is only 810mAh/g, which shows that the high-current cycle performance of the material is relatively general. In addition, the method disclosed by the document is prepared by chemical deposition of materials, not only is time-consuming, but also the production amount of each batch is small, and the method is difficult to be widely applied and popularized in industrial production.
In Electrochimica acta 218 (2016: 243-; the authors used ZIF-67 as a template to attach cobalt disulfide to the template through a series of treatments, followed by washing the template with strong acid and finally curing to obtain the composite. Compared with the traditional carbon-sulfur composite material, the material has excellent electrochemical performance, and under the condition of high current of 0.5C, the capacity after 300 cycles still has the capacity of 600 mAh/g; the composite material has excellent chemical adsorption capacity to polysulfide and good long-cycle stability. However, the utilization rate of the material to sulfur in the lithium-sulfur battery is not high, the capacity is not fully exerted, and a lot of elemental sulfur exists in a 'dead sulfur' state in the battery and can not participate in the de-intercalation redox reaction of lithium ions; the yield of the composite material obtained by the method is low, the method is complex, a template needs to be sacrificed, and the industrial popularization and application are very difficult.
The prior lithium-sulfur battery cathode material has the problems of complex preparation process, low material preparation yield, general long cycle performance, low sulfur utilization rate and the like. Therefore, a simple preparation method is urgently needed to obtain the cobalt disulfide and sulfur composite cathode material with dual functions (chemical adsorption capacity and oxidation-reduction catalysis capacity).
Disclosure of Invention
The invention aims to provide a cobalt disulfide/carbon nanofiber/sulfur composite material with excellent chemical adsorption capacity and redox capacity.
In view of the above, the present application provides a cobalt disulfide/carbon nanofiber/sulfur composite material, which is composed of carbon nanofibers, cobalt disulfide nanoparticles and sulfur; the surface of the carbon nanofiber is compounded with cobalt disulfide nanoparticles which are closely and orderly arranged, and the carbon nanofiber and the cobalt disulfide nanoparticles form a corn rod-shaped structure; the sulfur is supported in the corn cob structure.
Preferably, the diameter of the carbon nanofiber is 1-3 mu m, the diameter of the cobalt disulfide nanoparticle is 10-30 nm, and the loading amount of sulfur is 2-10 mg-cm-2。
The application also provides a preparation method of the cobalt disulfide/carbon nanofiber/sulfur composite material, which comprises the following steps:
A) mixing cobalt salt, a sulfur source compound and porous carbon nanofibers in a solvent, and carrying out hydrothermal reaction to obtain an initial composite material;
B) and mixing the initial composite material with sulfur powder and then carrying out annealing treatment to obtain the cobalt disulfide/carbon nanofiber/sulfur composite material.
Preferably, the porous carbon nanofiber is obtained by activating and pore-forming carbon nanofiber; the method for activating and pore-forming the carbon nanofiber comprises the following specific steps:
soaking the carbon nanofibers in alkali liquor for 5-15 hours, and drying the soaked carbon aerogel at 40-150 ℃ for 5-18 hours;
placing the dried carbon aerogel in an inert gas environment for high-temperature heat treatment; the inert gas is one or two of nitrogen and nitrogen, the heat treatment temperature is 500-1000 ℃, and the heat treatment time is 0.5-8 h.
Preferably, the cobalt salt is selected from one or more of cobalt oxalate tetrahydrate, cobalt acetate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate and cobalt nitrate hexahydrate; the sulfur source compound is thiourea; the solvent is ethylene glycol.
Preferably, the mass ratio of the cobalt salt to the sulfur source compound is (0.01-5.5): 1; the ratio of the mass of the porous carbon nanofiber to the total mass of the cobalt salt and the sulfur source compound is 0.01-5: 1; the mass ratio of the sulfur powder to the initial composite material is (0.1-8): 1.
preferably, the temperature of the hydrothermal reaction is 100-200 ℃ and the time is 5-24 h.
Preferably, the annealing treatment comprises: the mixed mixture is sealed in vacuum, and the pressure is lower than 100 Pa.
Preferably, the temperature rise rate of the annealing treatment is 2-8 ℃/min, the temperature is 100-300 ℃, and the time is 1-25 h.
The application also provides a lithium-sulfur battery, which comprises a positive electrode and a negative electrode and is characterized in that the material of the positive electrode is the cobalt disulfide/carbon nanofiber/sulfur composite material or the cobalt disulfide/carbon nanofiber/sulfur composite material prepared by the preparation method.
The cobalt disulfide/carbon nanofiber/sulfur composite material provided by the application has a unique corn-shaped nanostructure, and is endowed with unique dual-functionalization characteristics: the carbon nanofiber is used as a conductive channel and a supporting framework, has good electronic conductivity, is beneficial to the electronic exchange of lithium ions and sulfur, and accelerates the reaction process; the cobalt disulfide nanoparticles grown on the surface of the carbon nanofibers have excellent semiconductor properties, show electrocatalytic conversion performance on sulfur and lithium sulfide after nanocrystallization design, and solve the problem of low reaction activity of sulfur and lithium sulfide in a lithium-sulfur battery; and the cobalt disulfide has strong chemical adsorption characteristics, has an adsorption limiting effect on polysulfide, inhibits the shuttle effect of polysulfide in the battery, and improves the cycle stability of the battery. Furthermore, the corn-shaped nanostructure of the composite material has high sulfur loading capacity, and the high sulfur loading means that the lithium-sulfur battery has higher energy density, and the endurance of the battery is favorably improved.
Drawings
FIG. 1 is a schematic flow diagram of the present invention for preparing a cobalt disulfide/carbon nanofiber/sulfur composite;
fig. 2 is an SEM photograph of the cobalt disulfide/carbon nanofiber/sulfur composite prepared in example 1 of the present invention;
fig. 3 is a transmission electron microscope image of the cobalt disulfide/carbon nanofiber/sulfur composite prepared in example 1 of the present invention;
figure 4 is an XRD pattern of cobalt disulfide/carbon nanofiber material prepared in example 2 of the present invention;
figure 5 is an XRD pattern of the cobalt disulfide/carbon nanofiber/sulfur composite prepared in example 2 of the present invention;
FIG. 6 is a graph of long cycle performance of the cobalt disulfide/carbon nanofiber/sulfur composite prepared in example 2 of the present invention as a positive electrode of a lithium sulfur battery;
fig. 7 is a spectral graph of the cobalt disulfide/carbon nanofiber/sulfur composite prepared in example 2 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the lack of cobalt dioxide and sulfur composite materials with dual functions (chemical adsorption capacity and oxidation-reduction catalytic capacity) in the lithium-sulfur battery in the prior art, the application provides a cobalt disulfide/carbon nanofiber/sulfur composite material, which takes porous carbon nanofibers as conductive and structural frameworks due to the special corn rod-shaped morphology, and cobalt sulfide nanoparticles which are closely arranged are uniformly grown on the porous carbon nanofibers and have high sulfur loading capacity, so that the composite material has the dual functions and excellent electrochemical performance. Specifically, the embodiment of the invention discloses a cobalt disulfide/carbon nanofiber/sulfur composite material which is composed of carbon nanofibers, cobalt disulfide nanoparticles and sulfur; the surface of the carbon nanofiber is compounded with cobalt disulfide nanoparticles which are closely and orderly arranged, and the carbon nanofiber and the cobalt disulfide nanoparticles form a corn rod-shaped structure; the sulfur is supported in the corn cob structure.
In the cobalt disulfide/carbon nanofiber/sulfur composite material, the carbon nanofiber is used as a conductive channel and a supporting framework, so that the carbon nanofiber has good electronic conductivity, is beneficial to electronic exchange of lithium ions and sulfur, and accelerates the reaction process; the diameter of the carbon nanofiber is 1-3 mu m. In the composite material, the cobalt disulfide nanoparticles grow on the surface of the carbon nanofiber, and the cobalt disulfide nanoparticles are connected one by one to form corn kernels taking the carbon nanofiber as a corn cob structure, so that the composite material has an obvious ordered array distribution structure and is free of obvious agglomeration. The cobalt disulfide nanoparticles have two functions in the composite material, namely a chemical adsorption effect on polysulfide generated by the lithium-sulfur battery, so that the shuttle effect of the polysulfide is greatly inhibited, and a chemical catalytic conversion effect on sulfur and lithium sulfide is realized, so that the utilization rate of the sulfur in the lithium-sulfur battery is improved. The diameter of the cobalt disulfide nano particles is 10-30 nm. The unique corn-shaped nano structure formed by the carbon nano fiber and the cobalt disulfide nano particles has very high sulfur loading capacity, and the high loading capacity can reach 2-10 mg-cm-2. The high sulfur load means that the lithium-sulfur battery has higher energy density, is beneficial to improving the endurance of the battery and solving the mileage anxiety. The realization of high sulfur loading benefits from the unique nanostructure design of the material and the preparation of the bi-functionalized cobalt disulfide nanoparticles, so that the lithium storage capacity of sulfur can be fully exerted.
The application also provides a preparation method of the composite material, and the specific flow is shown in fig. 1, namely the composite material with catalytic conversion and chemical adsorption, which is prepared by chemically activating the carbon nanofibers, growing cobalt disulfide on the surfaces of the porous carbon nanofibers, sulfurizing sulfur, and specifically comprises the following steps:
A) mixing cobalt salt, a sulfur source compound and porous carbon nanofibers in a solvent, and carrying out hydrothermal reaction to obtain an initial composite material;
B) and mixing the initial composite material with sulfur powder and then carrying out annealing treatment to obtain the cobalt disulfide/carbon nanofiber/sulfur composite material.
In the process of preparing the composite material, firstly, mixing cobalt salt, a sulfur source compound and porous carbon nanofibers in a solvent, and carrying out hydrothermal reaction to obtain an initial composite material; in the process, firstly, raw materials are prepared, and the porous carbon nanofiber is obtained by carbon nanofiber activated pore-forming, wherein the activated pore-forming is specifically chemical activated pore-forming, and specifically comprises the following steps:
soaking the carbon nanofibers in alkali liquor for 5-15 hours, and drying the soaked carbon aerogel at 40-150 ℃ for 5-18 hours;
placing the dried carbon aerogel in an inert gas environment for high-temperature heat treatment; the inert gas is one or two of nitrogen and nitrogen, the heat treatment temperature is 500-1000 ℃, and the heat treatment time is 0.5-8 h.
In the above process, the alkali solution is selected from alkali solutions well known to those skilled in the art, and in specific examples, the alkali solution is selected from potassium hydroxide solution with a concentration of 0.1mol/L to 3.8 mol/L.
After the porous carbon nanofiber is prepared, dissolving cobalt salt and a sulfur source compound in a solvent to obtain a uniform solution, mixing the porous carbon nanofiber with the solution, and carrying out water bath reaction to obtain an initial composite material; in the process, cobalt ions and a sulfur source compound are mutually attracted under the action of static electricity, and then nucleation growth is carried out on the nano holes on the surface of the porous carbon nano fiber, so that cobalt disulfide nano particles which are orderly arranged are formed on the surface of the carbon nano fiber, and a corn rod-shaped nano structure which takes the carbon nano fiber as a conductive channel and the cobalt disulfide nano particles as a catalyst and a chemical adsorbent is formed. The cobalt salt is well known to those skilled in the art, and illustratively, the cobalt salt is selected from one or more of cobalt oxalate tetrahydrate, cobalt acetate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate, and cobalt nitrate hexahydrate. The sulfur source compound is well known to those skilled in the art and in particular embodiments is selected from thiourea. The mass ratio of the cobalt salt to the sulfur source compound is (0.01-5.5): 1. the solvent is ethylene glycol. And in the process of mixing the cobalt salt and the sulfur source compound, the mixing temperature is 25-70 ℃, the mixing time is 5-60 min, and the mixture is continuously stirred in the process. The ratio of the mass of the porous carbon nanofiber to the total mass of the cobalt salt and the sulfur source compound is 0.01-5: 1. The temperature of the hydrothermal reaction is 100-200 ℃, and the time is 5-24 h; in a specific embodiment, the temperature of the hydrothermal reaction is 120-180 ℃ and the time is 8-12 h. After the reaction, filtering the obtained product, cleaning and drying to obtain a pure initial composite material; the filtration is suction filtration, the cleaning adopts one or more of ethanol, methanol, acetone and water, and the cleaning frequency is 1-5 times; the drying mode is drying in an oven, the drying temperature is 40-100 ℃, and the drying time is 5-48 hours.
After the initial composite material is obtained, mixing the initial composite material with sulfur powder and then carrying out annealing treatment to obtain a cobalt disulfide/carbon nanofiber/sulfur composite material; in this process, the initial composite is infiltrated with sulfur to achieve a high sulfur loading of the initial composite due to the special corn-rod-like structure of the initial composite. The mass ratio of the sulfur powder to the initial composite material is (0.1-8): 1. before the annealing treatment, the sulfur powder and the initial composite material are subjected to vacuum packaging, more specifically, the vacuum packaging adopts a quartz glass tube to seal the tube, and the pressure in the tube is lower than 100 Pa. The temperature rise rate of the annealing treatment is 2-8 ℃/min, the temperature is 100-300 ℃, and the time is 1-25 h.
In the preparation process, in order to ensure that the cobalt disulfide nanoparticles can uniformly and fully grow on the surface of the carbon nanofiber, the carbon nanofiber is fully soaked in a cobalt salt and sulfur source compound solution. Meanwhile, the porous carbon nanofiber is required to be fully dispersed in the solution so as to ensure uniform and firm growth. In addition, the internal pressure of the vacuum sealing pipe is lower than 100Pa, otherwise, a large amount of air is adsorbed in the porous corn cob composite material and can not be successfully removed, so that the sulfur substances are unevenly distributed in the composite material, the local accumulation is serious, and the electron and ion conduction rate is influenced.
The preparation method is simple, only needs two steps, namely A) solution standing reaction and B) vulcanization treatment, and has the advantages of mild reaction conditions, short preparation period and stable yield. The scanning electron microscope image of the composite material prepared in example 2, namely the cobalt disulfide/carbon nanofiber/sulfur composite cathode material is shown in fig. 2, and as can be seen from fig. 2, the nanostructure of the composite material is similar to that of a corn cob, and a large number of cobalt disulfide nanoparticles are densely and hemp-like and orderly arranged on the carbon nanofiber, as shown in fig. 2 (c); the diameter of the cobalt disulfide nano particle is about 15-25 nm, so that the contact area of the cobalt disulfide nano particle and sulfur is increased, and the catalytic reaction activity and the chemical adsorption capacity are improved. In order to clearly identify the carbon nanofibers and the cobalt disulfide nanoparticles on the surface of the carbon nanofibers, a transmission electron microscope test is performed on the material, as shown in fig. 3; the basic framework structure consisting of the cobalt disulfide nano particles and the carbon nano fibers can be clearly distinguished by the graph of 3; the cobalt disulfide nanoparticles are connected one by one to form corn kernels on a corn cob structure, and the corn kernels show an obvious ordered array distribution structure without obvious agglomeration. The phase confirmation of the cobalt disulfide nanoparticles adopts X-ray diffraction analysis, and as shown in fig. 4, the X-ray diffraction pattern of the cobalt disulfide/carbon nanofiber composite material is shown, so that the cobalt disulfide/carbon nanofiber composite material corresponds to a standard cobalt disulfide XRD card; the composite material is actually a cobalt disulfide material, and an XRD (X-ray diffraction) spectrum does not show other impurity diffraction peaks, so that the purity of the composite material is very high, and the composite material does not contain other impurity components; after sulfur is loaded, the final cobalt disulfide/carbon nanofiber/sulfur composite cathode material is obtained, and the diffraction pattern of XRD is shown in figure 5; obviously, after sulfurization, the diffraction peak of elemental sulfur is very obvious, and the diffraction peak intensity of sulfur is far higher than the crystal diffraction peak intensity of cobalt disulfide, which shows that the sulfur loading on the composite material is very large, and is beneficial to greatly improving the energy density of the lithium-sulfur battery.
To test the composites in lithium sulfurElectrochemical performance in a battery, the material is used as a positive electrode material, lithium metal is used as a counter electrode of the material, and a lithium-sulfur battery is obtained by assembling. FIG. 6 is a graph showing the long cycle performance of the composite material as a positive electrode of a lithium-sulfur battery, and it can be seen that the composite material exhibits a large current of 2.1mAcm-2And a high sulfur loading of 2.6mgcm-2The composite material can contribute a capacity of up to 930 mAh/g. Even under long-cycle testing of up to 450 circles, the material has no obvious capacity fading during the cycle, and shows excellent long-cycle stability and high sulfur utilization rate.
The excellent performances are all benefited from the unique structural design of the composite material and the excellent electrochemical catalytic capacity and chemical adsorption capacity of the composite material. These two functions are fully demonstrated by near-edge X-ray absorption spectroscopy testing of synchrotron radiation sources. The near-edge X-ray absorption spectrum of the synchrotron radiation source was tested in situ on a lithium-sulfur cell, and the spectral curve is shown in fig. 7. As can be seen from fig. 7(a), in the discharging stage of the lithium-sulfur battery, the characteristic absorption peak of elemental sulfur at 2471eV is completely disappeared, indicating that the elemental sulfur in the composite material is completely converted into the lithium sulfide phase; the characteristic absorption peak of the lithium sulfide is very obvious at 2472eV, which shows that the conversion from sulfur simple substance to the lithium sulfide is very thorough in the discharging process, and the utilization rate of the sulfur is extremely high. The cobalt disulfide/carbon nanofiber plays an important role in electrochemical catalytic conversion, accelerates the solid-solid conversion process from sulfur to lithium sulfide, reduces the potential barrier of conversion, and thus improves the conversion rate.
And then, in-situ test is carried out on the charging process of the lithium-sulfur battery by using a synchrotron radiation light source, and the results show that after the battery is charged to 2.8V, the characteristic peak of lithium sulfide slowly disappears, and the absorption peak of sulfur simple substance is enhanced, which indicates that the lithium-sulfur battery can be completely converted back in the charging stage and has good reversibility. The test result fully shows that the difunctional characteristics of the cobalt disulfide/carbon nanofiber are well reflected in the lithium-sulfur battery, and the electrochemical catalytic conversion effect between elemental sulfur and lithium sulfide and the adsorption effect on polysulfide are achieved, so that the sulfur utilization rate of the cobalt disulfide/carbon nanofiber/sulfur composite cathode material is improved, the energy density of the lithium-sulfur battery is favorably improved, and the lithium storage capacity of sulfur is further exerted. Experiments prove that the composite cathode material has a great application prospect of the cathode material of the lithium-sulfur battery and a great market prospect.
The cobalt disulfide/carbon nanofiber/sulfur composite material prepared by the method has a unique corn-shaped nano structure, and is endowed with a unique dual-functionalization characteristic; the carbon nanofiber is used as a conductive channel and a supporting framework, has good electronic conductivity, is beneficial to the electronic exchange of lithium ions and sulfur, and accelerates the reaction process; the cobalt disulfide nanoparticles grown on the surface of the carbon nanofibers have excellent semiconductor properties, show electrocatalytic conversion performance on sulfur and lithium sulfide after nanocrystallization design, and solve the problem of low reaction activity of sulfur and lithium sulfide in a lithium-sulfur battery; and the cobalt disulfide has strong chemical adsorption characteristics, has an adsorption limiting effect on polysulfide, inhibits the shuttle effect of polysulfide in the battery, and improves the cycle stability of the battery. Compared with the traditional cobalt disulfide/sulfur composite cathode material, the composite material has a dual-functional design, and the performance of the composite material is greatly improved by prescribing medicines aiming at two major problems of a lithium-sulfur battery.
The unique corn rod-shaped nano structure prepared by the invention has very high sulfur loading capacity, and the maximum sulfur loading capacity can reach 10 mg-cm-2Which is not possessed by other traditional cobalt disulfide/sulfur composite cathode materials. The high sulfur load means higher energy density of the lithium-sulfur battery, which is beneficial to improving the endurance of the battery and solving the mileage anxiety; the realization of high sulfur loading benefits from the unique nanostructure design of the material and the preparation of the bi-functionalized cobalt disulfide nanoparticles, so that the lithium storage capacity of sulfur can be fully exerted.
The preparation method is simple, good in repeatability and short in period. In the method, a mild and simple solvent standing reaction method is adopted, the yield of the obtained material is high, the required equipment is simple and easy to operate, the method can be popularized and produced in a large scale, the cost is low, the stability and the repeatability are good, and the method has good application and popularization possibility. Other traditional lithium-sulfur battery positive electrode material preparation methods, such as chemical vapor deposition methods, high-pressure hydrothermal reaction, electrostatic spinning technologies and other methods, have low yield, high production equipment requirements and long cycle, and are not beneficial to large-scale industrial popularization and use.
For further understanding of the present invention, the following examples are given to illustrate the preparation method and application of the cobalt disulfide/carbon nanofiber/sulfur composite material provided by the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
Soaking 1.2g of carbon nanofiber in 0.15mol/L potassium hydroxide solution for 12 hours, then taking out the carbon nanofiber, drying the carbon nanofiber in a forced air drying oven at the drying temperature of 50 ℃ for 12 hours, and carrying out heat treatment on the dried carbon aerogel at the temperature of 800 ℃ for 2 hours under the argon condition to obtain a porous carbon nanofiber material;
adding 0.8g of porous carbon nanofiber into 50mL of mixed solution of cobalt oxalate tetrahydrate, thiourea and ethylene glycol, wherein the mass of the cobalt oxalate tetrahydrate and the mass of the thiourea are 0.43g and 0.27g respectively, and the volume of the ethylene glycol is 50mL, and stirring and mixing uniformly in advance; then placing the mixture in a water bath kettle for standing reaction, wherein the water bath temperature is 160 ℃, and the reaction time is 12 hours; and after the reaction is finished, carrying out suction filtration on the precipitate, washing the precipitate for 2 times by using ethanol, drying the precipitate in a 60 ℃ oven for 12 hours, mixing the dried precipitate with 0.6g of sulfur powder, grinding the mixture, carrying out vacuum packaging, putting a vacuum quartz tube in a muffle furnace for annealing treatment at the annealing temperature of 200 ℃ for 12 hours, and finally obtaining the cobalt disulfide/carbon nanofiber/sulfur composite material.
An SEM image of the composite material obtained in this example is shown in fig. 2, and as can be seen from fig. 2, the diameter of the carbon nanofiber serving as a conductive main channel is about 1.5 to 2 μm, and a large number of cobalt disulfide nanoparticles are densely and hemp-orderly arranged on the carbon nanofiber, as shown in fig. two (c); and the diameter of the cobalt disulfide nano particle is about 15-25 nm, so that the contact area with sulfur is increased, and the catalytic reaction activity and the chemical adsorption capacity are improved.
The transmission electron microscope image of fig. 3 clearly shows the structural features of the composite; as can be seen from fig. 3, the basic skeleton structure formed by the cobalt disulfide nanoparticles and the carbon nanofibers can be clearly distinguished, the carbon nanofibers are covered with dark black cobalt disulfide nanospheres, the nanospheres are mutually overlapped but do not agglomerate, that is, the cobalt disulfide nanoparticles are connected one by one to form "corn kernels" on the structure of the "corn cob", and the obvious ordered array distribution structure is shown, so that the synergistic catalytic and adsorption capacities of the nanospheres are improved, the catalytic reaction capacity of the lithium-sulfur battery is favorably enhanced, and the electrochemical performance is improved.
The material is assembled into a lithium-sulfur battery, the electrochemical performance of the lithium-sulfur battery is tested, and the first circle capacity of the lithium-sulfur battery is up to 980mAh/g at a high multiplying power of 0.5C, and the capacity fading is lower than 5% in a cycle of up to 540 circles, so that the lithium-sulfur battery has excellent lithium storage capacity.
Example 2
Soaking 0.5g of carbon nanofiber in 0.3mol/L potassium hydroxide solution for 12 hours, then taking out the carbon nanofiber and drying the carbon nanofiber in a forced air drying oven at the drying temperature of 50 ℃ for 12 hours, and carrying out heat treatment on the dried carbon aerogel at the temperature of 900 ℃ for 4 hours under the argon condition to obtain a porous carbon nanofiber material;
adding 0.4g of porous carbon nanofiber into 70mL of mixed solution of cobalt oxalate tetrahydrate, thiourea and ethylene glycol, wherein the mass of the cobalt oxalate tetrahydrate and the mass of the thiourea are 0.52g and 0.35g respectively, adding the ethylene glycol with the volume of 70mL, and stirring and mixing uniformly in advance; and then placing the mixture in a water bath kettle for standing reaction, wherein the water bath temperature is 180 ℃, the reaction time is 12 hours, after the reaction is finished, carrying out suction filtration on the precipitate, washing the precipitate for 2 times by using acetone, drying the precipitate in a 60 ℃ oven for 12 hours, mixing and grinding the obtained initial composite material and 0.6g of sulfur powder, carrying out vacuum packaging, placing a vacuum quartz tube in a muffle furnace for annealing treatment, wherein the annealing temperature is 250 ℃, and the heat preservation time is 12 hours, thus finally obtaining the cobalt disulfide/carbon nanofiber/sulfur composite material.
As shown in fig. 4, fig. 4 is an XRD pattern of the initial composite material, and as can be seen from fig. 4, the material corresponds to a standard XRD card of cobalt disulfide, which indicates that the composite material is actually cobalt disulfide material, and the XRD pattern does not show diffraction peaks of other impurities, and has high purity and no components of other impurities.
The X-ray diffraction pattern of the composite material obtained in this example is shown in fig. 5, and it can be seen from the pattern that the diffraction peak of the obtained composite positive electrode material perfectly corresponds to XRD of standard cobalt disulfide crystals and standard elemental sulfur, which indicates that the synthesized composite material has a complete cobalt disulfide crystal structure and a crystal form of elemental sulfur, and no other impurities exist; and the diffraction peak signal of the elemental sulfur is obviously higher than that of the cobalt disulfide, which shows that the composite material has high sulfur loading capacity and is beneficial to increasing the energy density of the lithium-sulfur battery.
Assembling the composite material obtained in the embodiment into a lithium-sulfur battery, and testing the electrochemical performance of the lithium-sulfur battery; FIG. 6 shows that the material is used for high current of 2.1mAcm-2And a high sulfur loading of 2.6mgcm-2Under the conditions of (a), the composite material can contribute a capacity of up to 930 mAh/g; even under the long-cycle test of 450 circles, the material has no obvious capacity attenuation in the cycle process, and shows excellent long-cycle stability and high sulfur utilization rate; these are all benefited from the unique structural design of the composite material, and its excellent electrochemical catalytic and chemisorption capabilities. The two functions are fully proved through a near-edge X-ray absorption spectrum test of a synchrotron radiation light source; the near-edge X-ray absorption spectrum of the synchrotron radiation light source is used for carrying out in-situ test on the lithium-sulfur battery, the spectral curve of the lithium-sulfur battery is shown in fig. 7, and as can be seen from fig. 7(a), in the discharging stage of the lithium-sulfur battery, the characteristic absorption peak of elemental sulfur at 2471eV completely disappears, which indicates that the elemental sulfur in the composite material is completely converted into a lithium sulfide phase; the characteristic absorption peak of the lithium sulfide is very obvious at 2472eV, which shows that the conversion from sulfur simple substance to the lithium sulfide is very thorough in the discharging process, and the utilization rate of the sulfur is extremely high.
The cobalt disulfide/carbon nanofiber plays an important role in electrochemical catalytic conversion, accelerates the solid-solid conversion process from sulfur to lithium sulfide, reduces the potential barrier of conversion, and thus improves the conversion rate. And then, in-situ test is carried out on the charging process of the lithium sulfide battery by using a synchrotron radiation light source, and the results show that after the battery is charged to 2.8V, the characteristic peak of the lithium sulfide slowly disappears, and the absorption peak of the elemental sulfur is enhanced, so that the lithium sulfide can be completely converted back in the charging stage, and the lithium sulfide battery has good reversibility. The test result fully shows that the difunctional characteristics of the cobalt disulfide/carbon nanofiber are well reflected in the lithium-sulfur battery, and the electrochemical catalytic conversion effect between elemental sulfur and lithium sulfide and the adsorption effect on polysulfide are achieved, so that the sulfur utilization rate of the cobalt disulfide/carbon nanofiber/sulfur composite cathode material is improved, the energy density of the lithium-sulfur battery is favorably improved, and the lithium storage capacity of sulfur is further exerted.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A cobalt disulfide/carbon nanofiber/sulfur composite material is composed of carbon nanofibers, cobalt disulfide nanoparticles and sulfur; the surface of the carbon nanofiber is compounded with cobalt disulfide nanoparticles which are closely and orderly arranged, and the carbon nanofiber and the cobalt disulfide nanoparticles form a corn rod-shaped structure; the sulfur is supported in the corn cob structure.
2. The cobalt disulfide/carbon nanofiber/sulfur composite material according to claim 1, wherein the diameter of the carbon nanofiber is 1 to 3 μm, and the cobalt disulfide nanofiber has a diameter of 1 to 3 μmThe diameter of the particles is 10-30 nm, and the loading amount of the sulfur is 2-10 mg-cm-2。
3. A method of making the cobalt disulfide/carbon nanofiber/sulfur composite of claim 1 comprising the steps of:
A) mixing cobalt salt, a sulfur source compound and porous carbon nanofibers in a solvent, and carrying out hydrothermal reaction to obtain an initial composite material;
B) and mixing the initial composite material with sulfur powder and then carrying out annealing treatment to obtain the cobalt disulfide/carbon nanofiber/sulfur composite material.
4. The preparation method according to claim 3, characterized in that the porous carbon nanofiber is obtained by activating and pore-forming carbon nanofiber; the method for activating and pore-forming the carbon nanofiber comprises the following specific steps:
soaking the carbon nanofibers in alkali liquor for 5-15 hours, and drying the soaked carbon aerogel at 40-150 ℃ for 5-18 hours;
placing the dried carbon aerogel in an inert gas environment for high-temperature heat treatment; the inert gas is one or two of nitrogen and nitrogen, the heat treatment temperature is 500-1000 ℃, and the heat treatment time is 0.5-8 h.
5. The method according to claim 3, wherein the cobalt salt is selected from one or more of cobalt oxalate tetrahydrate, cobalt acetate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate, and cobalt nitrate hexahydrate; the sulfur source compound is thiourea; the solvent is ethylene glycol.
6. The production method according to claim 3, wherein the mass ratio of the cobalt salt to the sulfur source compound is (0.01 to 5.5): 1; the ratio of the mass of the porous carbon nanofiber to the total mass of the cobalt salt and the sulfur source compound is 0.01-5: 1; the mass ratio of the sulfur powder to the initial composite material is (0.1-8): 1.
7. the preparation method according to claim 3, wherein the hydrothermal reaction is carried out at a temperature of 100 to 200 ℃ for 5 to 24 hours.
8. The method according to claim 3, wherein the annealing treatment comprises: the mixed mixture is sealed in vacuum, and the pressure is lower than 100 Pa.
9. The preparation method according to claim 3, wherein the temperature rise rate of the annealing treatment is 2-8 ℃/min, the temperature is 100-300 ℃, and the time is 1-25 h.
10. A lithium-sulfur battery, which comprises a positive electrode and a negative electrode, wherein the material of the positive electrode is the cobalt disulfide/carbon nanofiber/sulfur composite material as defined in any one of claims 1 to 2 or the cobalt disulfide/carbon nanofiber/sulfur composite material prepared by the preparation method as defined in any one of claims 3 to 9.
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